JP6024259B2 - Novel naphthalaldehyde compound, process for producing the same, and process for producing triarylamine compounds from the compound - Google Patents

Description

  The present invention relates to a novel 2-halogenated aryl-1-naphthalaldehyde compound and a process for producing the same. Furthermore, the present invention relates to a method for producing a triarylamine compound from this 2-halogenated aryl-1-naphthalaldehyde compound.

  The 2-halogenated aryl-1-naphthalaldehyde compound of the present invention can be used as an intermediate for various derivatives. In particular, it is useful as an intermediate for medical and agricultural chemicals and an intermediate for electronic materials. Specifically, it is very important because it is used as an intermediate for synthesizing the compounds described in International Patent Publication No. 2007/119800 pamphlet and Japanese Patent Application Laid-Open No. 2011-012047.

  As the 2-halogenated aryl-1-naphthalaldehyde compound, 2- (4-fluorophenyl) -1-naphthalaldehyde and a production method thereof are disclosed (for example, see Patent Document 1). However, 2-halogenated aryl-1-naphthalaldehyde compounds other than 2- (4-fluorophenyl) -1-naphthalaldehyde are not known. The above disclosed 2- (4-fluorophenyl) -1-naphthalaldehyde is produced according to the following reaction scheme, and the production process is a boronic acid compound with many reaction steps and low pot efficiency. Because it goes through, it is not industrially satisfactory.

  Further, as a compound having a structure close to 2-halogenated aryl-1-naphthalaldehyde, (1E) -N- (4-methoxyphenyl) -1- (3-phenylnaphthalen-2-yl) ethanimine and its production A method is disclosed (for example, see Non-Patent Document 1).

  It has been reported that a halogenated benzo [a] fluorenone derivative or a halogenated benzo [a] fluorene derivative important as an electronic material and a pharmaceutical intermediate can be synthesized by a process including the following reaction scheme (for example, Patent Document 2). reference). In the manufacturing process including this reaction scheme, an expensive boronic acid compound and trifluoromethanesulfonic anhydride are used, which is industrially disadvantageous.

  In addition, in the said process, reaction of parachlorophenyl boronic acid progressed and there existed a subject that a compound with high environmental impact, such as a chlorobiphenyl compound, was easy to byproduce, and the improvement was calculated | required.

  Patent Document 4 describes a method for producing a triarylamine compound useful for an organic EL device by a process including the following reaction scheme. In this production process, trifluoromethanesulfonic acid anhydride, boronic acid Compounds, and sodium borohydride are used.

  However, since trifluoromethanesulfonic anhydride is highly corrosive and sodium borohydride is a water-inhibiting substance and highly toxic, handling it with great care. Therefore, establishment of an industrial process that does not use these compounds has been demanded.

Japanese translation of PCT publication No. 60-5000499 JP 2009-114114 A International Patent Publication 2007/119800 Pamphlet JP 2011-012047 A

Organic Letters, Vol. 4, No. 10, pp. 1783-1785, 2002

  An object of the present invention is to provide a novel 2-halogenated aryl-1-naphthalaldehyde compound useful as an intermediate for medical and agricultural chemicals and an intermediate for electronic materials, and a method for producing the same.

  Still another object of the present invention is to use the above-described 2-halogenated aryl-1-naphthalaldehyde compound as a production intermediate, and from the compound described in International Publication No. 2007/119800 pamphlet and JP2011-012047A. The object is to provide a method for synthesizing a triarylamine compound.

  The present invention provides a 2-halogenated aryl-1-naphthalaldehyde compound represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. R ¹ The substitution position of is not limited as long as it is other than the 1-position and the 2-position, Ar is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or phenyl A phenylene group which may have a group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a naphthylene which may have a phenyl group X ¹ represents an iodine atom, a bromine atom or a chlorine atom.
Furthermore, the present invention is represented by the general formula (1), characterized by hydrolyzing a 2-halogenated aryl-1-naphthylaldimine compound represented by the following general formula (6) in the presence of an acid. A method for producing a 2-halogenated aryl-1-naphthalaldehyde compound is provided.

(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. R ¹ The substitution position of is not limited as long as it is other than the 1-position and the 2-position, and R ² is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or A phenyl group which may have a phenyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or an arylalkyl group having 7 to 18 carbon atoms, Ar is a straight chain having 1 to 18 carbon atoms. A branched or cyclic alkyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkoxy group or a phenylene group optionally having a phenyl group, or a straight chain, branched or cyclic alkyl group having 1 to 18 carbon atoms. Group, .X ¹ representing a linear, it may naphthylene group which may have a branched or cyclic alkoxy group or a phenyl group having 1 to 18 carbon atoms represents a iodine atom, a bromine atom or a chlorine atom.)
Furthermore, the present invention provides another method for producing the 2-halogenated aryl-1-naphthalaldehyde compound represented by the above general formula (1) in the presence of a transition metal catalyst and a base. Characterized by reacting a 1-naphthylaldimine compound represented by the following general formula (3) with a dihalogenated aromatic compound, and then hydrolyzing the reaction product in the presence of an acid: A method for producing a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is provided.

(In the formulas (1), (2), (3) and (6), R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a straight chain having 1 to 18 carbon atoms. Represents a chain, branched or cyclic alkoxy group or phenyl group, and the substitution position of R ¹ is not limited as long as it is other than the 1-position and 2-position, R ² is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, A linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a phenyl group optionally having a phenyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or an arylalkyl having 7 to 18 carbon atoms Ar represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenylene group which may have a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a phenyl group, or carbon number To 18 linear, branched or cyclic alkyl group, .X ¹ and X ² represents a straight-chain, may naphthylene group which may have a branched or cyclic alkoxy group or a phenyl group having 1 to 18 carbon atoms, each independently Represents an iodine atom, a bromine atom or a chlorine atom.)
Furthermore, the present invention produces a halogenated benzofluorene compound or a halogenated dibenzofluorene compound represented by the general formula (c) from the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1). Then, a method for producing a triarylamine compound represented by the general formula (Y) from the halogenated benzofluorene compound or the halogenated dibenzofluorene compound is provided.

(In the formulas (1), (c) and (Y), Ar ¹ and Ar ² each independently have 6 to 40 carbon atoms which may have a substituent having 1 to 18 carbon atoms or a halogen atom. of .R ¹ representing the heteroaryl group an aryl group or a substituent or may 5-40 carbon atoms which may have a halogen atom having 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, having 1 to 18 carbon atoms It represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group, and the substitution position of R ¹ is limited unless it is in the 1-position and 2-position. R ³ and R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, Substituents having 1 to 18 carbon atoms Or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent having 1 to 18 carbon atoms or a halogen atom. X ¹ represents an iodine atom, a bromine atom or a chlorine atom, Ar represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group A phenylene group which may have a C 1-18 linear, branched or cyclic alkyl group, a C 1-18 linear, branched or cyclic alkoxy group or a naphthylene group which may have a phenyl group In formula (c) and formula (Y)

Represents a phenylene group or a naphthylene group fused to an adjacent 5-membered ring, and the phenylene group and the naphthylene group are each a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. It may have at least one substituent selected from a linear, branched or cyclic alkoxy group or a phenyl group. )

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the above general formula (1) of the present invention can be used as an intermediate of various derivatives. In particular, it is useful as an intermediate for medical and agricultural chemicals and an intermediate for electronic materials. Specifically, it is important as an intermediate for synthesizing a triaryl compound useful as a constituent material of an organic EL device described in International Publication No. 2007/119800 pamphlet and Japanese Patent Application Laid-Open No. 2011-012047.

  According to the method for producing a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) according to the present invention, the 2-halogenated aryl-1-naphthalaldehyde compound is highly selected. And can be manufactured efficiently.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is a halogenated benzo [a] fluorenone derivative or halogenated compound useful as an intermediate for electronic materials and an intermediate for pharmaceuticals. It can be used as a raw material for producing a benzo [a] fluorene derivative.

  When the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is used, a halogenated benzo [a] fluorenone derivative and a halogenated benzo which are useful as an intermediate for pharmaceutical intermediates and electronic materials [A] A fluorene derivative can be produced without using an expensive boronic acid compound and trifluoromethanesulfonic anhydride, and suppressing the production of by-products with high environmental impact such as a chlorobiphenyl compound.

  Furthermore, using the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) as a production intermediate, the triarylamine compound represented by the general formula (Y) is produced. According to the method, the triarylamine compound represented by the general formula (Y) can be produced industrially advantageously. That is, for example, it is represented by the general formula (Y) without using trifluoromethanesulfonic anhydride and sodium borohydride used in the production process described in Patent Document 4, and with fewer steps than in the past. Triarylamine compounds can be produced.

₃ is a chart showing ¹ H-NMR (CDCl ₃ ) measurement results of 1- (4-methoxyphenyliminomethyl) naphthalene obtained in Synthesis Example 1. FIG. 2 is a chart showing ¹ H-NMR (CDCl ₃ ) measurement results of 2- (4-chlorophenyl) -1-naphthalaldehyde obtained in Example 1. FIG. 2 is a chart showing ¹³ C-NMR (CDCl ₃ ) measurement results of 2- (4-chlorophenyl) -1-naphthalaldehyde obtained in Example 1. FIG. 2 is a chart showing ¹ H-NMR (CDCl ₃ ) measurement results of 2- (4-bromophenyl) -1-naphthalaldehyde obtained in Example 3. FIG. 6 is a chart showing ¹³ C-NMR (CDCl ₃ ) measurement results of 2- (4-bromophenyl) -1-naphthalaldehyde obtained in Example 3. FIG.

In the 2-halogenated aryl-1-naphthalaldehyde compound represented by the above general formula (1) according to the present invention, R ¹ is a hydrogen atom, a hydroxyl group, a linear, branched or cyclic group having 1 to 18 carbon atoms. An alkyl group, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group.

R ¹ is a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group.

Linear 1 to 18 carbon atoms R ^1, as the branched or cyclic alkyl group is not particularly limited, for example, a methyl group, an ethyl group, n- propyl group, Isopuroiru group, cyclopropyl group, n- butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 2-ethylbutyl group, 4-methylpentyl group, n-heptyl Group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decanyl group, n-dodecanyl group, tetradecyl group, hexadecyl group, octadecyl group, trifluoromethyl group, trichloromethyl group and the like.

Linear 1 to 18 carbon atoms R ^1, as the branched or cyclic alkoxy group is not particularly limited, for example, a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, sec- butoxy Group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, trifluoromethoxy group, trichloromethoxy group and the like.

R ¹ is preferably a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or a phenyl group, from the viewpoint of easy availability of raw materials, and more preferably a hydrogen atom.

  Ar represented by the general formula (1) may have a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. It is a naphthylene group which may have a phenylene group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group.

In Ar, the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is not particularly limited. For example, the linear, branched or cyclic group having 1 to 18 carbon atoms represented by R ¹ in the general formula (1) is used. The same substituent as the alkyl group can be exemplified, and the linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms is not particularly limited. For example, the number of carbon atoms represented by R ¹ in the general formula (1) The same substituents as those of 1 to 18 linear, branched or cyclic alkoxy groups can be exemplified.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) hydrolyzes the 2-halogenated aryl-1-naphthylaldimine compound represented by the following general formula (6) in the presence of an acid. It is synthesized by decomposing.

(In the formula, R ¹ , Ar and X ¹ represent the same group as in general formula (1). The substitution position of R ¹ is not limited as long as it is other than positions 1 and 2. R ² has 1 to 18 carbon atoms. A linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a phenyl group optionally having a phenyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms Or an arylalkyl group having 7 to 18 carbon atoms.)
In the general formula (6), R ² may have a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. A phenyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms.

In R ² , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group that may have a phenyl group, 1 to 18 carbon atoms The linear, branched or cyclic alkyl group is not particularly limited, and examples thereof include the same substituents as the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R ¹ in the general formula (1). The linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms is not particularly limited. For example, the linear or branched chain having 1 to 18 carbon atoms represented by R ¹ in the general formula (1) Or the same substituent as a cyclic alkoxy group can be illustrated.

Linear 1 to 18 carbon atoms R ^2, as the branched or cyclic alkyl group is not particularly limited, for example, straight-chain having 1 to 18 carbon atoms shown by R ¹ of Formula (1), branched or cyclic The same substituent as an alkyl group can be illustrated.

The aryl alkyl group having 7 to 18 carbon atoms R ^2, is not particularly limited, for example, benzyl group, phenethyl group, a phenyl hexyl group, etc. naphthylmethyl group.

Specific examples of R ² are not particularly limited. For example, phenyl group, 2-methylphenyl group, 2-methoxyphenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 4-methylphenyl group , 4-methoxyphenyl group and the like can be raised. Among these, a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group are preferable, and a 4-methoxyphenyl group is particularly preferable in terms of easy raw material procurement and easy synthesis.

  The 2-halogenated aryl-1-naphthylaldimine compound represented by the general formula (6) is not particularly limited. For example, 2- (4-chlorophenyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (4-Bromophenyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (4-iodophenyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (3-chlorophenyl)- 1- (4-methoxyphenyliminomethyl) naphthalene, 2- (3-bromophenyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (3-iodophenyl) -1- (4-methoxyphenylimino Methyl) naphthalene, 4-methoxy-2- (4-chlorophenyl) -1- (4-methoxyphenylimino) Til) naphthalene, 4-methoxy-2- (4-bromophenyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 4-methoxy-2- (4-iodophenyl) -1- (4-methoxyphenylimino) Methyl) naphthalene, 2- (4-chloro-1-naphthyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (4-bromo-1-naphthyl) -1- (4-methoxyphenyliminomethyl) Naphthalene, 2- (4-iodo-1-naphthyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (6-chloro-2-naphthyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (6-Bromo-2-naphthyl) -1- (4-methoxyphenyliminomethyl) naphthalene, 2- (6-iodo-2-naphthyl) ) -1- (4-methoxyphenyl imino methyl) naphthalene.

  The hydrolysis reaction of the 2-halogenated aryl-1-naphthylaldimine compound represented by the general formula (6) is usually performed by contacting and mixing the 2-aryl-1-naphthylaldimine compound and an aqueous acid solution. .

  Although it does not specifically limit as an acid, For example, organic acids, such as inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, or an acetic acid, an oxalic acid, p-toluenesulfonic acid, formic acid, are used, Usually 2-aryl-1- An amount of acid is used that makes the mixture of the naphthylaldimine compound and the aqueous acid solution acidic. Of these, hydrochloric acid is preferable as the acid, and it is preferable to use an amount such that the mixture of the 2-aryl-1-naphthylaldimine compound and the aqueous acid solution has a pH of 3 or less.

  The hydrolysis reaction is usually performed in a temperature range of 10 to 100 ° C., and the reaction time is usually in the range of several minutes to 24 hours, although it varies depending on the reaction temperature and the amount of acid. If reaction temperature is 10 degreeC or more, reaction will fully advance, and if it is 100 degrees C or less, it is economically preferable.

  The hydrolysis reaction may be performed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is inert to the reaction. Usually, hydrocarbons such as hexane and cyclohexane, aromatic solvents such as toluene and xylene, tetrahydrofuran, diethyl ether, Examples include ether solvents such as dimethoxyethane and cyclopentyl methyl ether, and aprotic organic solvents such as dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone. The amount of organic solvent used is not particularly limited.

  In the hydrolysis reaction, the raw materials can be added to the reaction vessel in several batches to react, or two or more raw materials can be added to the reaction vessel alternately or simultaneously, and intermittently or continuously. It can also be made.

  After the hydrolysis reaction, an organic layer containing a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is obtained by adding an organic solvent insoluble in water and performing an extraction treatment. By concentrating the obtained organic layer, the 2-halogenated aryl-1-naphthalaldehyde compound can be taken out.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) can be isolated and purified by operations such as recrystallization and silica gel chromatography, if necessary.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is not particularly limited, and examples thereof include 2- (4-chlorophenyl) -1-naphthalaldehyde, 2- (4- Bromophenyl) -1-naphthalaldehyde, 2- (4-iodophenyl) -1-naphthalaldehyde, 2- (3-chlorophenyl) -1-naphthalaldehyde, 2- (3-bromophenyl) -1- Naphthalaldehyde, 2- (3-iodophenyl) -1-naphthalaldehyde, 4-methoxy-2- (4-chlorophenyl) -1-naphthalaldehyde, 4-methoxy-2- (4-bromophenyl)- 1-naphthalaldehyde, 4-methoxy-2- (4-iodophenyl) -1-naphthalaldehyde, 2- (4-chloro-1-naphthyl) -1-naphtha Aldehyde, 2- (4-bromo-1-naphthyl) -1-naphthalaldehyde, 2- (4-iodo-1-naphthyl) -1-naphthalaldehyde, 2- (6-chloro-2-naphthyl)- Examples include 1-naphthalaldehyde, 2- (6-bromo-2-naphthyl) -1-naphthalaldehyde, 2- (6-iodo-2-naphthyl) -1-naphthalaldehyde, and the like.

  The 2-halogenated aryl-1-naphthylaldimine compound represented by the general formula (6) is a 1-naphthylaldimine compound represented by the following general formula (2) and the following general formula in the presence of a transition metal catalyst and a base. It can synthesize | combine by making the dihalogenated aromatic compound represented by (3) react (arylation reaction).

(In the formula, R ¹ , R ² , Ar and X ¹ represent the same group as in general formula (1) or (6). The substitution position of R ¹ is not limited as long as it is other than the 1-position and 2-position. ² represents an iodine atom, a bromine atom or a chlorine atom.)
The 1-naphthylaldimine compound represented by the general formula (2) is not particularly limited, and examples thereof include 1-methyliminomethylnaphthalene, 1-isopropyliminomethylnaphthalene, 1- (tert-butyliminomethyl) naphthalene, 1 -(N-hexyliminomethyl) naphthalene, 1-cyclohexyliminomethylnaphthalene, 1- (n-octyliminomethyl) naphthalene, 1- (n-dodecyliminomethyl) naphthalene, 1-benzyliminomethylnaphthalene, 1-phenethylimino Examples include methylnaphthalene, 1-phenyliminomethylnaphthalene, 1- (4-methoxyphenyliminomethyl) naphthalene.

  The compound represented by the general formula (3) is not particularly limited. For example, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dibromobenzene, 1, 3-dibromobenzene, 1,4-dibromobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 2-bromochlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene 2-bromoiodobenzene, 3-bromoiodobenzene, 4-bromoiodobenzene, 2-iodochlorobenzene, 3-iodochlorobenzene, 4-iodochlorobenzene, 1,4-dichloronaphthalene, 2,6-dichloronaphthalene, 1, 4-dibromonaphthalene, 1,4-diiodonaphthalene, 1,8-diiodonaphth Ren, 2,6-diiodo-naphthalene, 2,7-diiodo-naphthalene, 1,3-diiodo-naphthalene, 1,6-diiodo naphthalene.

  Although it does not specifically limit as a transition metal catalyst used for arylation reaction, For example, a rhodium catalyst and a ruthenium catalyst can be mentioned.

  Although it does not specifically limit as a rhodium catalyst, For example, acetylacetonaphthobis (ethylene) rhodium (I), acetylacetonato bis (1,5-cyclooctene) rhodium (I), bis (1,5-cyclooctadiene) ) Rhodium (I) tetrafluoroborate, chlorobis (cyclooctene) rhodium (I) dimer, chlorocarbonylbis (triphenylphosphine) rhodium (I), chloro (1,5-cyclooctadiene) rhodium (I) dimer, chlorotris (Triphenylphosphine) rhodium (I), hydridocarbonyltris (triphenylphosphine) rhodium (I), rhodium acetate (II) dimer, rhodium (III) chloride, rhodium (III) acetylacetonate and the like.

  The ruthenium catalyst is not particularly limited. For example, bis (cyclopentadienyl) ruthenium (0), bis (ethylcyclopentadienyl) ruthenium (II), carbonylchlorohydridotris (triphenylphosphine) ruthenium (II) , Carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloro (1,5-cyclooctadiene) (pentamethylcyclopentadienyl) ruthenium (II), chloro (cyclopentadienyl) bis (triphenyl) Phosphine) ruthenium (II), dichloro (benzene) ruthenium (II) dimer, dichloro (p-cymene) ruthenium (II) dimer, dichloro (p-cymene) tricyclohexylphosphine ruthenium (II), dichlorodicarbonylbi (Triphenylphosphine) ruthenium (II), dichloro tris (triphenylphosphine) ruthenium (II), ruthenium (III) acetylacetonate, ruthenium chloride (III), and the like iodide ruthenium (III) is.

The amount of the transition metal catalyst used is not particularly limited as long as the reaction proceeds smoothly, but is usually 0.01 to 10 mol% in terms of the number of moles of transition metal with respect to the 1-naphthylaldimine compound. If it is 0.01 mol% or more, reaction will fully advance, and if it is 10 mol% or less, it is economically preferable.
These transition metal catalysts may contain a known ligand. Examples of the ligand include, but are not limited to, tri (n-butyl) phosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, tri (furyl) phosphine, 2-dicyclohexylphosphino-biphenyl, 2-di (tert-butyl) phosphino-biphenyl, 2-dicyclohexylphosphino-2′-dimethylaminobiphenyl, 2-dimethylaminomethyl-1-bis (di-tert-butylphosphino) ) Ferrocene, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) butane, bis (diphenylphosphino) ferrocene, 2,2′-bis (diphenylphosphino) -1,1 '-Naphthyl, 9, -Phosphine compounds such as dimethyl-4,5-bis (diphenylphosphino) xanthene, 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazolium tetrafluoroborate, 1,3-bis ( 2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene, 1,3-bis (2,6-diisopropylphenyl) imidazolium chloride, 1,3-bis (2,6-diisopropylphenyl) imidazole 2-ylidene, 1,3-bis (1-adamantyl) imidazolium chloride, 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazolium tetrafluoroborate, 1,3- Carbene compounds such as bis (2,4,6-trimethylphenyl) imidazolium chloride It can gel.

  Of these, triarylphosphine compounds such as triphenylphosphine are preferable in that the desired product can be obtained in high yield.

  The content of the ligand is preferably in the range of 0.5 to 10 moles, more preferably in the range of 1 to 4 moles, relative to the number of moles of transition metal contained in the transition metal catalyst. If it is 0.5 times mole or more, reaction will fully advance, and if it is 10 times mole or less, it is economically preferable.

The base used in the arylation reaction is not particularly limited, but examples thereof include sodium carbonate, sodium acetate, sodium hydroxide, potassium carbonate, potassium acetate, potassium hydroxide, potassium phosphate, cesium carbonate, cesium acetate, cesium hydroxide and the like. Alkaline metal bases, alkaline earth metal bases such as calcium hydroxide, calcium carbonate, barium hydroxide, barium carbonate and the like can be mentioned. The amount of the base used is 1 to 10 times mol for 1 mol of 1-naphthylaldimine compound. The range of 1 to 5 times mol is more preferable. If it is 1 time mole or more, reaction will fully advance, and if it is 10 times mole or less, it is economically preferable.

  The arylation reaction is usually performed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is inert to the reaction. Usually, hydrocarbons such as hexane and cyclohexane, aromatic solvents such as toluene and xylene, tetrahydrofuran, diethyl ether, Examples include ether solvents such as dimethoxyethane and cyclopentyl methyl ether, and aprotic organic solvents such as dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone.

  The reaction temperature and reaction time of the arylation reaction vary depending on the amounts of 1-naphthylaldimine compound, dihalogenated aromatic compound, transition metal catalyst, base and organic solvent used, but are usually 0 to 200 ° C. and 1 to 72, respectively. Selected from a range of time. If the reaction temperature is 0 ° C. or higher, the reaction proceeds sufficiently, and if it is 200 ° C. or lower, it is economically preferable.

  In the arylation reaction, the raw material can be added to the reaction vessel in several batches and reacted, or two or more raw materials can be added to the reaction vessel alternately or simultaneously, and intermittently or continuously. It can also be made.

  In the reaction of the 1-naphthylaldimine compound represented by the general formula (2) and the dihalogenated aromatic compound represented by the general formula (3) (arylation reaction) in the presence of a transition metal catalyst and a base, it is surprising. In particular, a 2-halogenated aryl-1-naphthylaldimine compound represented by the general formula (6) was synthesized with high selectivity.

  The 1-naphthylaldimine compound represented by the general formula (2) is prepared from a corresponding naphthalaldehyde compound represented by the general formula (4) and a primary amine compound represented by the following general formula (5) by a known method, for example, It can be easily synthesized by heating in the presence of no catalyst or acid catalyst (see, for example, the method described in JP-T-2008-546642).

(In the formula, R ¹ and R ² are the same as the substituents represented by the general formula (1) or (6). The substitution position of R ¹ is not limited as long as it is other than the 1-position and 2-position.)
The naphthalaldehyde compound represented by the general formula (4) is not particularly limited, and examples thereof include 1-naphthalaldehyde, 4-methoxy-1-naphthalaldehyde, and 5,8-dihydroxy-1-naphthalaldehyde. 7-methoxy-1-naphthalaldehyde, 8-methoxy-1-naphthalaldehyde, 4- (benzyloxy) -1-naphthalaldehyde and the like.

  Although it does not specifically limit as a primary amine compound represented by General formula (5), For example, a methylamine, an ethylamine, n-propylamine, isopropyl amine, n-butylamine, sec-butylamine, tert-butylamine, n -Aliphatic amines such as hexylamine, cyclohexylamine, n-octylamine, n-dodecylamine, benzylamine, phenethylamine, 6-phenylhexylamine, 1-naphthylmethylamine, aniline, o-toluidine, m-toluidine, Aromatic amines such as p-toluidine, o-anisidine, m-anisidine, p-anisidine and the like can be mentioned.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is derived into a carboxylic acid by Pinnick oxidation using, for example, a known sodium chlorite, and further known as polyphosphoric acid. It can be derived into a halogenated benzo [a] fluorenone derivative by an acid catalyst (see, for example, JP-A-2009-114114).

(In the formula, R ¹ and X ¹ represent the same group as in the general formula (1). Ar represents a phenylene group.)
The benzo [a] fluorenone derivative and its reduced benzo [a] fluorene derivative have a functional group such as a halogen atom or a ketone group, so that more useful compounds such as organic EL materials and liquid crystal materials can be used. It can be converted into electronic materials and medical and agrochemical compounds.

  More specifically, if a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) of the present invention is used, a compound represented by the general formula (1) of JP2011-012047 A Can be synthesized with a smaller number of steps compared to a conventionally known production method.

(Wherein R ¹ , R ² and X ¹ represent the same definition as described above. Ar ¹ and Ar ² may each independently have a substituent having 1 to 18 carbon atoms or a halogen atom. An aryl group having 6 to 40 carbon atoms, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or a halogen atom having 1 to 18 carbon atoms, R ³ and R ⁴ are each independently A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituent having 1 to 18 carbon atoms or a halogen atom. Represents an aryl group having 6 to 40 carbon atoms which may have, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or halogen atom having 1 to 18 carbon atoms. Bromine atom or chlorine source Ar represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenylene group which may have a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a phenyl group, or carbon (It represents a naphthylene group optionally having a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group.)
The reaction of naphthalene to 1-naphthalaldehyde (one step) is described, for example, in Journal of the Chemical Society, pages 339-346, 1936.

  The reaction of naphthalene to 2-hydroxy-1-acetonaphthone (3 steps) is, for example, Journal of Organic Chemistry, Vol. 56, Item 21, pages 6148-6151, 1991 and Asian Journal of Chemistry, Vol. 5, Item 4, 831-835, 1993.

  Furthermore, the present invention produces a halogenated benzofluorene compound or a halogenated dibenzofluorene compound represented by the general formula (c) from the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1). Then, a method for producing a triarylamine compound represented by the general formula (Y) is provided.

(In the formula, Ar ¹ and Ar ² are each independently a substituent having 1 to 18 carbon atoms or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or 1 to 18 carbon atoms. may have a substituent or a halogen atom represents a heteroaryl group which may having 5 to 40 carbon atoms .R ¹ is a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, carbon atoms 1 to 18 represents a linear, branched or cyclic alkoxy group, or a phenyl group, and the substitution position of R ¹ is not limited as long as it is other than the 1-position and the 2-position, and R ³ and R ⁴ are each independently A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituent having 1 to 18 carbon atoms or a halogen atom Have Or an aryl group having 6 to 40 carbon atoms, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or halogen atom having 1 to 18 carbon atoms, X ¹ represents an iodine atom or a bromine atom; Or a chlorine atom, Ar represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenylene group optionally having a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group; Or a straight-chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, a straight-chain, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a naphthylene group that may have a phenyl group. In (Y)

Represents a phenylene group or a naphthylene group fused to an adjacent 5-membered ring, and the phenylene group and the naphthylene group are each a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. It may have at least one substituent selected from a linear, branched or cyclic alkoxy group or a phenyl group. )
A method for producing a halogenated benzofluorene compound or a halogenated dibenzofluorene compound represented by the general formula (c) from a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) of the present invention The method for producing the triarylamine compound represented by the general formula (Y) from the halogenated benzofluorene compound or the halogenated dibenzofluorene compound represented by the general formula (c) is not particularly limited. For example, known methods described in Patent Document 3, Patent Document 4, and the like can be used.

  In addition, the halogenated benzofluorene compound or the halogenated dibenzofluorene compound represented by the general formula (c) is produced from the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1). Although it does not specifically limit as a method of manufacturing the triarylamine compound represented by a formula (Y), For example, the manufacturing method containing the following process A-process D is mentioned.

Step A: a step of obtaining a compound represented by the general formula (a) by reacting a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) with a carbon nucleophile;
Step B: A step of obtaining a compound represented by the general formula (b) by reacting the compound represented by the general formula (a) obtained in the step A with an acid catalyst;
Step C: a step of reacting the compound represented by the general formula (b) obtained in Step B with an alkyl halide to obtain a compound represented by the general formula (c); and Step D: obtained in Step C The compound represented by general formula (c) is reacted with an arylamine compound to obtain a compound represented by general formula (Y).

(In the formula, Ar ¹ and Ar ² are each independently a substituent having 1 to 18 carbon atoms or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or 1 to 18 carbon atoms. may have a substituent or a halogen atom represents a heteroaryl group which may having 5 to 40 carbon atoms .R ¹ is a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, carbon atoms 1 to 18 represents a linear, branched or cyclic alkoxy group, or a phenyl group, and the substitution position of R ¹ is not limited as long as it is other than the 1-position and the 2-position, and R ³ and R ⁴ are each independently A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituent having 1 to 18 carbon atoms or a halogen atom Have Or an aryl group having 6 to 40 carbon atoms, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or halogen atom having 1 to 18 carbon atoms, X ¹ represents an iodine atom or a bromine atom; Or a chlorine atom, Ar represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenylene group optionally having a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group; Or a straight-chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, a straight-chain, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a naphthylene group that may have a phenyl group, represented by the general formula (c) and In general formula (Y)

Represents a phenylene group or a naphthylene group fused to an adjacent 5-membered ring, and the phenylene group and the naphthylene group are each a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. It may have at least one substituent selected from a linear, branched or cyclic alkoxy group or a phenyl group. )
In General Formula (Y), Ar ¹ and Ar ² are each independently a substituent having 1 to 18 carbon atoms or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or 1 carbon atom. Represents a heteroaryl group having 5 to 40 carbon atoms which may have a substituent of -18 or a halogen atom. Although the said C1-C18 substituent is not specifically limited, For example, a methyl group, an ethyl group, n-butyl group, a tert- butyl group, a benzyl group, a phenethyl group, a trifluoromethyl group (above) , Alkyl group having 1 to 18 carbon atoms), methoxy group, ethoxy group, n-butoxy group, tert-butoxy group, benzyloxy group, trifluoromethoxy group (above, alkoxy group having 1 to 18 carbon atoms), phenyl group , Biphenylyl group, naphthyl group, fluorenyl group (above, aromatic hydrocarbon group having 1 to 18 carbon atoms), phenoxy group, naphthoxy group, fluorenyloxy group (above, aromatic oxy group having 1 to 18 carbon atoms) , Pyridyl group, quinolyl group, benzoimidazolyl group, furanyl group, dibenzofuranyl group, thiazolyl group, thienyl group, dibenzothienyl group (above, carbon 1-18 heteroaromatic hydrocarbon groups), diphenylamino groups, phenyltolylamino groups, naphthylphenylamino groups, biphenylylphenylamino groups (above, diarylamino groups having 1-18 carbon atoms), cyano groups, etc. Can be mentioned. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

The aryl group having 6 to 40 carbon atoms in Ar ¹ and Ar ² is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, and a chrysenyl group. Group, perylenyl group, picenyl group, benzo [a] fluorenyl group, benzo [b] fluorenyl group, benzo [c] fluorenyl group and the like. Among these, an aryl group having 6 to 18 carbon atoms is preferable in consideration of molding stability by a vacuum deposition method. These aryl groups may have a plurality of substituents having 1 to 18 carbon atoms or halogen atoms.

The heteroaryl group having 5 to 40 carbon atoms in Ar ¹ and Ar ² is an aromatic ring group containing at least one hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and is not particularly limited. Are, for example, quinolyl group, pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzoimidazolyl group, dibenzofuranyl group, dibenzothienyl group and the like. Among these, a heteroaryl group having 5 to 18 carbon atoms is preferable in consideration of molding stability by a vacuum deposition method. These heteroaryl groups may have a plurality of the above-mentioned substituents having 1 to 18 carbon atoms or halogen atoms.

In the general formula (Y), R ³ and R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, branched or It may have a cyclic alkoxy group, a C1-C18 substituent or a C6-C40 aryl group which may have a halogen atom, or a C1-C18 substituent or a halogen atom. A good heteroaryl group having 5 to 40 carbon atoms is represented.

In R ³ and R ^4, a straight-chain having 1 to 18 carbon atoms, and branched or cyclic alkyl group is not particularly limited, for example, a methyl group, an ethyl group, n- propyl group, Isopuroiru group, a cyclopropyl radical, n -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 2-ethylbutyl group, 4-methylpentyl group N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decanyl group, n-dodecanyl group, tetradecyl group, hexadecyl group, octadecyl group, trifluoromethyl group, trichloromethyl group, etc. Can be mentioned.

In R ³ and ^{R 4,} a straight-chain having 1 to 18 carbon atoms, and branched or cyclic alkoxy group is not particularly limited, for example, a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group , Sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, trifluoromethoxy group, trichloromethoxy group and the like.

R ¹ is preferably a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or a phenyl group, from the viewpoint of easy availability of raw materials, and more preferably a hydrogen atom.

An aryl group having 6 to 40 carbon atoms which may have a substituent having 1 to 18 carbon atoms or a halogen atom represented by R ³ and R ⁴ , or a substituent or halogen atom having 1 to 18 carbon atoms In the heteroaryl group having 5 to 40 carbon atoms which may be present, the substituent having 1 to 18 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-butyl group, a tert- Butyl group, benzyl group, phenethyl group, trifluoromethyl group (above, alkyl group having 1 to 18 carbon atoms), methoxy group, ethoxy group, n-butoxy group, tert-butoxy group, benzyloxy group, trifluoromethoxy group (Above, an alkoxy group having 1 to 18 carbon atoms), phenyl group, biphenylyl group, naphthyl group, fluorenyl group (above, an aromatic hydrocarbon group having 1 to 18 carbon atoms), phenol Noxy group, naphthoxy group, fluorenyloxy group (above, C1-C18 aromatic oxy group), pyridyl group, quinolyl group, benzimidazolyl group, furanyl group, dibenzofuranyl group, thiazolyl group, thienyl group, dibenzo Thienyl group (above, C1-C18 heteroaromatic hydrocarbon group), diphenylamino group, phenyltolylamino group, naphthylphenylamino group, biphenylylphenylamino group (above, C1-C18 diarylamino group) ), A cyano group, and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

  In addition, the aryl group having 6 to 40 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, and a perylenyl group. , Picenyl group, benzo [a] fluorenyl group, benzo [b] fluorenyl group, benzo [c] fluorenyl group, and the like. Among these, an aryl group having 6 to 18 carbon atoms is preferable in consideration of molding stability by a vacuum deposition method. These aryl groups may have a plurality of substituents having 1 to 18 carbon atoms or halogen atoms.

  Further, the heteroaryl group having 5 to 40 carbon atoms is an aromatic ring group containing at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and is not particularly limited. Examples include quinolyl group, pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzoimidazolyl group, dibenzofuranyl group, dibenzothienyl group and the like. Among these, a heteroaryl group having 5 to 18 carbon atoms is preferable in consideration of molding stability by a vacuum deposition method. These heteroaryl groups may have a plurality of the above-mentioned substituents having 1 to 18 carbon atoms or halogen atoms.

  In step A, the 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is reacted with a carbon nucleophile in the presence of an organic solvent.

  The carbon nucleophile is not particularly limited. For example, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium bromide, ethylmagnesium iodide, isopropylmagnesium bromide, cyclopentylmagnesium bromide, phenylmagnesium bromide. And organic magnesium compounds such as methyl lithium, ethyl lithium, n-butyl lithium, and phenyl lithium, and organic zinc compounds such as diethyl zinc.

  The solvent is not particularly limited as long as it is inert to the reaction. Usually, ether solvents such as tetrahydrofuran, diethyl ether, dimethoxyethane, and cyclopentyl methyl ether, and hydrocarbons such as hexane and cyclohexane. And aromatic solvents such as toluene and xylene.

  The reaction temperature and reaction time vary depending on the amounts of 2-halogenated aryl-1-naphthalaldehyde compound, carbon nucleophile, and organic solvent used, but are usually −80 to 150 ° C. and 1 to 48 hours, respectively. It is chosen from the range. If reaction temperature is 0 degreeC or more, reaction will fully advance, and if it is 100 degrees C or less, it is economically preferable, and reaction time has the preferable range for 1 to 24 hours.

  The amount of carbon nucleophile used is usually preferably in the range of 1 to 10 moles per mole of 2-halogenated aryl-1-naphthalaldehyde compound, and 1 to 3 times from the viewpoint of suppressing by-products. A molar range is more preferred.

  Step A can be performed under normal pressure, in an inert gas atmosphere such as nitrogen or argon, or under pressure.

  About process B-D, it can carry out similarly to the method of Unexamined-Japanese-Patent No. 2011-012047.

  The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

In the examples, the apparatus and conditions used for the measurement are as follows.
[ ¹ H, ¹³ C-NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Mass spectrometry]
Measuring device: M-80B manufactured by Hitachi, Ltd.
[Gas chromatography measurement]
Device: GC-17A manufactured by Shimadzu Corporation
Column: capillary column (GL Science NB-5)
Carrier gas: helium Column temperature: 150 ° C → 10 ° C / min → 300 ° C
Injection: 280 ° C
Detector: FID
[HPLC analysis]
Equipment: Multi-station LC-8020 manufactured by Tosoh Corporation
Column: Inertsil ODS-3V (4.6 mmΦ × 250 mm)
Detector: UV detection (wavelength 254 nm)
Eluent: methanol / tetrahydrofuran = 9/1 (v / v ratio)
Synthesis Example 1 Synthesis of 1- (4-methoxyphenyliminomethyl) naphthalene 1-Naphthalaldehyde 10.89 g (69.7 mmol), p-anisidine 10.23 g (69.7 mmol), and ethanol 150 mL in a 300 mL eggplant type flask Under a nitrogen atmosphere and heated to reflux for 4 hours. After concentration of the reaction solution, 18.2 g of a light brown viscous oil was obtained (yield = 100%, GC purity = 97.5%. After several days, it gradually crystallized). It was confirmed by ¹ H-NMR (FIG. 1) that it was the desired product (1- (4-methoxyphenyliminomethyl) naphthalene).

¹ H-NMR (CDCl ₃ ) δ (ppm): 9.13 (s, 1H), 9.02 (d, 1H, J = 8.4 Hz), 8.08 (d, 1H, J = 7.0 Hz) ), 7.93 (t, 2H, J = 8.4 Hz), 7.50-7.64 (m, 3H), 7.32 (d, 2H, J = 9.2 Hz), 6.97 (d , 2H, J = 9.2 Hz), 3.84 (s, 3H)
Example 1 Synthesis of 2- (4-chlorophenyl) -1-naphthalaldehyde, Part 1
A concentrated solution of 1- (4-methoxyphenyliminomethyl) naphthalene obtained in Synthesis Example 1 2.0 g (7.42 mmol), 1.71 g (8.91 mmol) of p-bromochlorobenzene, dichloro (p-cymene) ruthenium (II) Dimer 113 mg (0.18 mmol, corresponding to 2.5 mol% of 1- (4-methoxyphenyliminomethyl) naphthalene), triphenylphosphine 194 mg (0.74 mmol), potassium carbonate 2.04 g (14.8 mmol) And 20 mL of N-methylpyrrolidone was added to a 100 mL eggplant-shaped flask and reacted at 100 ° C. for 20 hours under a nitrogen atmosphere.

After cooling, 50 mL of toluene and 40 mL of H ₂ O were added to extract the organic layer. The organic layer was washed with saturated brine and then concentrated. The organic layer was stirred at room temperature after adding 20 mL of tetrahydrofuran and 25 mL of 10% aqueous hydrochloric acid. Tetrahydrofuran was distilled off, and 30 mL of toluene was added to extract the organic layer. The organic layer was washed with H ₂ O and saturated brine, and dried over magnesium sulfate. Thereafter, the obtained organic layer was concentrated and further purified by silica gel chromatography (hexane / toluene = 2/1 volume ratio) to obtain 1.82 g of a pale yellow solid (yield = 92%). .

From the ¹ H and ¹³ C-NMR of the pale yellow solid, it was identified that the obtained compound was 2- (4-chlorophenyl) -1-naphthalaldehyde.

¹ H-NMR (CDCl ₃ ) δ (ppm): 10.2 (s, 1H), 9.22 (d, 1H, J = 8.0 Hz), 8.08 (d, 1H, J = 8.4 Hz) ), 7.91 (d, 1H, J = 7.8 Hz), 7.75-7.35 (m, 7H) (see FIG. 2)
¹³ C-NMR (CDCl ₃ ) δ (ppm): 194.01, 146.29, 137.03, 134.65, 134.02, 132.98, 131.64, 130.20, 129.32, 128 .82, 128.51, 128.22, 127.85, 126.90, 125.65 (see FIG. 3)
Example 2 Synthesis of 2- (4-chlorophenyl) -1-naphthalaldehyde, Part 2
Instead of the dichloro (p-cymene) ruthenium (II) dimer used in Example 1, 71 mg (0.07 mmol, 1- (4-methoxyphenyliminomethyl) naphthalene of dichlorotris (triphenylphosphine) ruthenium (II) (Corresponding to 1 mol%) and without using triphenylphosphine, the same experiment as in Example 1 was performed to obtain 1.78 g of 2- (4-chlorophenyl) -1-naphthalaldehyde (yield) = 90%).

Example 3 Synthesis of 2- (4-bromophenyl) -1-naphthalaldehyde, Part 1
A concentrated solution of 1- (4-methoxyphenyliminomethyl) naphthalene obtained in Synthesis Example 1 2.0 g (7.42 mmol), 7.0 g (29.7 mmol) of p-dibromobenzene, dichlorotris (triphenylphosphine) Ruthenium (II) 71 mg (0.07 mmol, corresponding to 1 mol% of 1- (4-methoxyphenyliminomethyl) naphthalene), potassium carbonate 2.04 g (14.8 mmol) and N-methylpyrrolidone 40 mL in a 100 mL eggplant type flask In addition, the reaction was performed at 100 ° C. for 20 hours in a nitrogen atmosphere.

  Post-treatment was performed according to Example 1 to obtain 1.54 g of 2- (4-bromophenyl) -1-naphthalaldehyde (yield = 64%). As a result of mass spectrometry, it was confirmed to be the target product (molecular weight = 310).

¹ H-NMR (CDCl ₃ ) δ (ppm): 10.2 (s, 1 H), 9.22 (d, 1 H, J = 8.4 Hz), 8.08 (d, 1 H, J = 8.8 Hz) ), 7.92 (d, 1H, J = 8.2 Hz), 7.70-7.25 (m, 7H) (see FIG. 4)
¹³ C-NMR (CDCl ₃ ) δ (ppm): 193.85, 146.18, 137.43, 133.93, 132.89, 131.85, 131.37, 130.11, 129.24, 128 .70, 128.13, 127.69, 126.83, 125.56, 122.76 (see FIG. 5)
Example 4 Synthesis of 2- (4-bromophenyl) -1-naphthalaldehyde, Part 2
Instead of p-bromochlorobenzene used in Example 1, 2.52 g (8.91 mmol) of p-bromoiodobenzene was used, and 45 mg (0.07 mmol, 1-dimer) of dichloro (p-cymene) ruthenium (II) dimer was used. (Corresponding to 1.0 mol% of (4-methoxyphenyliminomethyl) naphthalene) and 73 mg (0.28 mmol) of triphenylphosphine, an experiment similar to that of Example 1 was performed, and 2.01 g of 2- (4-bromo Phenyl) -1-naphthalaldehyde was obtained (yield = 87%).

^{From 1} H and ¹³ C-NMR, it was identified that the obtained compound was 2- (4-bromophenyl) -1-naphthalaldehyde of Example 3.

¹ H-NMR (CDCl ₃ ) δ (ppm): 10.2 (s, 1 H), 9.22 (d, 1 H, J = 8.4 Hz), 8.08 (d, 1 H, J = 8.8 Hz) ), 7.92 (d, 1H, J = 8.2 Hz), 7.70-7.25 (m, 7H)
¹³ C-NMR (CDCl ₃ ) δ (ppm): 193.87, 146.20, 137.45, 133.95, 132.91, 131.86, 131.39, 130.12, 129.26, 128 71, 128.15, 127.69, 126.84, 125.58, 122.78
Example 5 Synthesis of 9-chlorobenz [a] fluoren-11-one 0.5 g (1.87 mmol) of 2- (4-chlorophenyl) -1-naphthalaldehyde obtained in Example 1, 10 mL of t-butanol, 2-methyl-2-butene 0.56 g (7.99 mmol), tetrahydrofuran 8 mL, H ₂ O 2 mL, sodium chlorite 0.54 g (6.0 mmol), sodium dihydrogen phosphate 0.36 g (3.0 mmol) ) Was stirred at room temperature for 4 hours. After concentration, 30 mL of toluene and 10 mL of H ₂ O were added to separate the layers. After concentrating the organic layer, 12.0 g of polyphosphoric acid was charged into the obtained concentrated liquid, and the mixture was heated and stirred at 130 ° C. for 21 hours. After cooling the reaction solution, 80 ml of toluene and 50 ml of water were added for liquid separation. The obtained organic layer was washed with water until neutral. After drying with magnesium sulfate, the organic layer was concentrated. The obtained residue was recrystallized from ethyl acetate to obtain 0.28 g of reddish brown crystals. As a result of ¹ H-NMR measurement, it was confirmed to be 9-chlorobenz [a] fluoren-11-one described in JP-A-2009-114114.

Example 6 Synthesis of 1- (1-hydroxy) ethyl-2- (4-chlorophenyl) naphthalene 2- (4-chlorophenyl) -1-naphthalaldehyde obtained in Example 1 1.00 g (3.74 mmol) Then, 8 mL of tetrahydrofuran was added to a 100 mL eggplant type flask under a nitrogen atmosphere, and the temperature of the reaction solution was cooled to 0 ° C. Thereafter, 3.2 mL of methylmagnesium bromide (1.4 mol / L toluene / tetrahydrofuran solution) was added dropwise. Furthermore, after stirring at room temperature for 2 hours, 5 mL of 5% aqueous hydrochloric acid was added dropwise to complete the reaction. After toluene was added to extract the organic layer, the organic layer was washed with H ₂ O and saturated brine, dried with magnesium sulfate, and then the solvent was distilled off to obtain 1.01 g of a pale yellow solid. As a result of ¹ H-NMR measurement, it was confirmed to be 1- (1-hydroxy) ethyl-2- (4-chlorophenyl) naphthalene described in International Patent Publication 2007/119800 pamphlet and JP2011-012047.

Example 7 Synthesis of N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) phenylamine Example using 19.0 g (122 mmol) of 1-naphthalaldehyde as a starting material According to the method 4, 37.9 g (HPLC purity 93.5%) of 2- (4-bromophenyl) -1-naphthalaldehyde was synthesized.

  1 in the same manner as in Example 6 except that 2- (4-bromophenyl) -1-naphthalaldehyde was used unpurified instead of 2- (4-chlorophenyl) -1-naphthalaldehyde. 39.8 g (HPLC purity 94.2%) of-(1-hydroxy) ethyl-2- (4-bromophenyl) naphthalene was synthesized.

  Furthermore, instead of 1- (1-hydroxy) ethyl-2- (4-chlorophenyl) naphthalene, the obtained 1- (1-hydroxy) ethyl-2- (4-bromophenyl) naphthalene was used. N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) phenylamine was synthesized by the same method as described in Synthesis Example 0 and Synthesis Example 1 and Example 2.

  To 39.8 g of the crude 1- (1-hydroxy) ethyl-2- (4-bromophenyl) naphthalene obtained above, 160 mL of dichloromethane was added and cooled to 0 ° C., and then sulfuric acid (boron trifluoride · 23.9 g (244 mmol) (changed from diethyl etherate) was added dropwise and stirred at room temperature for 1 hour.

After the reaction was completed by adding 40 mL of H ₂ O, 195 g of a 10% aqueous sodium hydroxide solution (488 mmol as sodium hydroxide) was added dropwise with stirring to neutralize. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated to give 34.4 g (HPLC purity 93.5%) of a brown viscous oil. ^The product was confirmed to be 9-bromo-11-methyl-11H-benzo [a] fluorene by ¹ H-NMR measurement, and the product was directly used in the next reaction without purification.

The obtained 9-bromo-11-methyl-11H-benzo [a] fluorene (34.4 g, 111 mmol), benzyltriethylammonium chloride (25.3 g, 111 mmol) and methyl iodide (31.6 g, 222 mmol) were added to dimethyl sulfoxide (282 mL). After dissolution and cooling to 0 ° C., 27.8 g of a 48% aqueous sodium hydroxide solution (333 mmol as sodium hydroxide) was added dropwise with stirring. After stirring at room temperature for 1 hour, 100 mL of H ₂ O and 230 mL of toluene were added, and then the organic layer was washed. After drying with magnesium sulfate, the extract was concentrated, and the resulting residue was purified by recrystallization to obtain 26.4 g (HPLC purity 94.1%) of pale yellow crystals. As a result of ¹ H-NMR measurement, it was confirmed to be 9-bromo-11,11-dimethyl-11H-benzo [a] fluorene.

The obtained 9-bromo-11,11-dimethyl-11H-benzo [a] fluorene 6.63 g (20.5 mmol), aniline 0.93 g (9.98 mmol), sodium tert-butoxide 2.40 g (25. 0 mmol), palladium acetate 32 mg (0.14 mmol, corresponding to 1.4 mol% of aniline), tri-tert-butylphosphine 113 mg (0.56 mmol) and o-xylene 68 mL were added, and the mixture was stirred at 140 ° C for 15 hours. After completion of the reaction, 17 mL of H ₂ O was added, stirred at room temperature for 0.5 hours and allowed to stand, and then the aqueous layer was separated. After drying with magnesium sulfate, the extract was concentrated, and the resulting residue was purified by recrystallization instead of silica gel column chromatography to obtain 2.71 g (HPLC purity 99.9%) of pale yellow crystals. It was.

  As a result of mass spectrometry, it was confirmed that it was N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) phenylamine described in JP2011-012047A (Example 2). did.

Example 8 Synthesis of 2- [N-phenyl-N- (4-biphenylyl) amino] 11,11′-dimethyl-11H-benzo [a] fluorene Instead of aniline used in Example 7, N-phenyl- 2.45 g (9.98 mmol) of N-4-biphenylylamine was used, 3.32 g (10.3 mmol) of 9-bromo-11,11-dimethyl-11H-benzo [a] fluorene, and 16 mg (0. 07 mmol, corresponding to 0.7 mol% of aniline), 57 mg (0.28 mmol) of tri-tert-butylphosphine, and 60 mL of o-xylene, and the same experiment as in Example 8 was carried out to obtain 2.23 g of pale yellow crystals. (HPLC purity 99.9%) was obtained.

  As a result of mass spectrometry, it is 2- [N-phenyl-N- (4-biphenylyl) amino] 11,11′-dimethyl-11H-benzo [a] fluorene described in JP2011-012047A (Example 1). It was confirmed.

Example 9 Synthesis of N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) -p-tolylamine p-toluidine 1 instead of aniline used in Example 7 A similar experiment was conducted except that 0.07 g (9.98 mmol) was used, and the resulting residue was purified by silica gel column chromatography to obtain 4.13 g (HPLC purity 99.9%) of pale yellow crystals. It was.

  As a result of mass spectrometry, it is N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) -p-tolylamine described in JP2011-012047A (Example 3). It was confirmed.

Example 10 Synthesis of N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) -4-pyridylamine 4-amino instead of aniline used in Example 7 A similar experiment was conducted except that 0.94 g (9.98 mmol) of pyridine was used, and 2.60 g (HPLC purity 99.9%) of pale yellow crystals were obtained.

  As a result of mass spectrometry, it is N, N′-bis (11,11′-dimethyl-11H-benzo [a] fluoren-9-yl) -4-pyridylamine described in JP2011-012047A (Example 4). It was confirmed.

  The novel 2-halogenated aryl-1-naphthalaldehyde compound represented by the above general formula (1) of the present invention can be used as an intermediate for various derivatives. In particular, it is useful as an intermediate for medical and agricultural chemicals and an intermediate for electronic materials. Specifically, it is important as an intermediate for synthesizing a triaryl compound useful as a constituent material of an organic EL device described in International Publication No. 2007/119800 pamphlet and Japanese Patent Application Laid-Open No. 2011-012047.

  The 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) is a halogenated benzo [a] fluorenone derivative or halogenated compound useful as an intermediate for electronic materials and an intermediate for pharmaceuticals. It can be used as a raw material for producing a benzo [a] fluorene derivative. If a 2-halogenated aryl-1-naphthalaldehyde compound represented by the formula (1) is used as a starting material, these halogenated benzo [a] fluorenone derivatives and halogenated benzo [a] fluorene derivatives can be produced at low cost. And it can manufacture by suppressing the production | generation of a by-product with high environmental impact.

  Furthermore, organic compounds described in International Publication No. 2007/119800 pamphlet and Japanese Patent Application Laid-Open No. 2011-012047 using 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1) as a starting material. A triaryl compound useful as a constituent material of an EL element can be advantageously produced industrially. That is, for example, a triarylamine compound is synthesized in a high yield without using the trifluoromethanesulfonic anhydride and sodium borohydride used in the production process described in Patent Document 4 and with fewer steps. be able to. Waste reduction and environmental impact reduction associated with improved yield are achieved.

Claims (15)

A 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1).

(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. R ¹ The substitution position of is not limited as long as it is other than the 1-position and the 2-position, Ar is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or phenyl A phenylene group which may have a group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a naphthylene which may have a phenyl group X ¹ represents an iodine atom, a bromine atom or a chlorine atom. 2. The method according to claim 1, wherein in general formula (1), R ¹ is a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group, or a phenyl group, and Ar is a phenylene group or a naphthylene group. Halogenated aryl-1-naphthalaldehyde compounds. 2. The 2-halogenated aryl-1-naphthalaldehyde compound according to claim 1, wherein in general formula (1), R ¹ is a hydrogen atom and Ar is a phenylene group. 2-halogenated aryl-1 represented by the general formula (1), wherein the 2-halogenated aryl-1-naphthylaldimine compound represented by the general formula (6) is hydrolyzed in the presence of an acid. -Manufacturing method of a naphthalaldehyde compound.

(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. R ¹ The substitution position of is not limited as long as it is other than the 1-position and the 2-position, and R ² is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or A phenyl group which may have a phenyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or an arylalkyl group having 7 to 18 carbon atoms, Ar is a straight chain having 1 to 18 carbon atoms. A branched or cyclic alkyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkoxy group or a phenylene group optionally having a phenyl group, or a straight chain, branched or cyclic alkyl group having 1 to 18 carbon atoms. Group, .X ¹ representing a linear, it may naphthylene group which may have a branched or cyclic alkoxy group or a phenyl group having 1 to 18 carbon atoms represents a iodine atom, a bromine atom or a chlorine atom.) In the general formulas (1) and (6), Ar is a phenylene group or a naphthylene group, and R ¹ is a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group, or a phenyl group. A process for producing the described 2-halogenated aryl-1-naphthalaldehyde compound. In the general formulas (1) and (6), Ar is a phenylene group or a naphthylene group, and R ¹ is a hydrogen atom. A method for producing a phthalaldehyde compound. In the presence of a transition metal catalyst and a base, the 1-naphthylaldimine compound represented by the general formula (2) is reacted with the dihalogenated aromatic compound represented by the general formula (3). A method for producing a 2-halogenated aryl-1-naphthalaldehyde compound represented by the general formula (1), wherein hydrolysis is performed in the presence of an acid.

(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a phenyl group. R ¹ The substitution position of is not limited as long as it is other than the 1-position and the 2-position, and R ² is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or A phenyl group which may have a phenyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or an arylalkyl group having 7 to 18 carbon atoms, Ar is a straight chain having 1 to 18 carbon atoms. A branched or cyclic alkyl group, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkoxy group or a phenylene group optionally having a phenyl group, or a straight chain, branched or cyclic alkyl group having 1 to 18 carbon atoms. Group, a straight-chain having 1 to 18 carbon atoms, .X ¹ and X ² represents an naphthylene group which may have a branched or cyclic alkoxy group or a phenyl group are each independently, an iodine atom, a bromine atom or a chlorine atom Represents.) In the general formulas (1), (2), (3), and (6), Ar is a phenylene group or a naphthylene group, and R ¹ is a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group, or a phenyl group. The method for producing a 2-halogenated aryl-1-naphthalaldehyde compound according to claim 7, characterized in that it is characterized in that The 2-halogenated compound according to claim 7, characterized in that, in the general formulas (1), (2), (3), and (6), Ar is a phenylene group and R ¹ is a hydrogen atom. A method for producing an aryl-1-naphthalaldehyde compound. The method for producing a 2-halogenated aryl-1-naphthalaldehyde compound according to any one of claims 7 to 9, wherein the transition metal catalyst is a rhodium catalyst or a ruthenium catalyst. The method for producing a 2-halogenated aryl-1-naphthalaldehyde compound according to any one of claims 7 to 9, wherein the transition metal catalyst is a ruthenium catalyst containing triphenylphosphine as a ligand. A halogenated benzofluorene compound or a halogenated dibenzofluorene compound represented by the general formula (c) is produced from the 2-halogenated aryl-1-naphthalaldehyde compound according to claim 1 , and then the halogenated benzofluorene A method for producing an arylamine compound represented by the general formula (Y), comprising obtaining a triarylamine compound represented by the following general formula (Y) from a compound or a halogenated dibenzofluorene compound.

(In the above formula, Ar ¹ and Ar ² are each independently a substituent having 1 to 18 carbon atoms or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or 1 to 18 carbon atoms. Or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent, or a halogen atom, R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, carbon It represents a linear, branched or cyclic alkoxy group of formula 1 to 18, or a phenyl group, and the substitution position of R ¹ is not limited as long as it is other than the 1-position and 2-position, and R ³ and R ⁴ are respectively Independently, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituent group or halogen having 1 to 18 carbon atoms Atom An aryl group having 6 to 40 carbon atoms which may have, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or halogen atom having 1 to 18 carbon atoms, X ¹ represents iodine. Represents an atom, a bromine atom or a chlorine atom, Ar may have a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms or a phenyl group; A good phenylene group, a straight chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, a straight chain, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a naphthylene group that may have a phenyl group is represented. (C) and in general formula (Y)

Represents a phenylene group or a naphthylene group fused to an adjacent 5-membered ring, and the phenylene group and the naphthylene group are each a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. It may have at least one substituent selected from a linear, branched or cyclic alkoxy group or a phenyl group. ) R ¹ is a hydrogen atom, Ar is a phenylene group, and in general formula (c) and general formula (Y)

The method for producing a triarylamine compound according to claim 12, wherein is a phenylene group fused to an adjacent 5-membered ring. A 2-halogenated aryl-1-naphthalaldehyde compound represented by the formula (1) is produced by the method according to claim 4 or 7, and then the 2-halogenated compound is produced by the method according to claim 12. A method for producing a triarylamine compound represented by the formula (Y), comprising producing a triarylamine compound represented by the following formula (Y) from an aryl-1-naphthalaldehyde compound.

(In the above formula, Ar ¹ and Ar ² are each independently a substituent having 1 to 18 carbon atoms or an aryl group having 6 to 40 carbon atoms which may have a halogen atom, or 1 to 18 carbon atoms. Or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent, or a halogen atom, R ¹ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, carbon It represents a linear, branched or cyclic alkoxy group of formula 1 to 18, or a phenyl group, and the substitution position of R ¹ is not limited as long as it is other than the 1-position and 2-position, and R ³ and R ⁴ are respectively Independently, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituent group or halogen having 1 to 18 carbon atoms Atom It represents an aryl group having 6 to 40 carbon atoms which may have, or a heteroaryl group having 5 to 40 carbon atoms which may have a substituent or halogen atom having 1 to 18 carbon atoms. ) And in general formula (Y)

Represents a phenylene group or a naphthylene group fused to an adjacent 5-membered ring, and the phenylene group and the naphthylene group are each a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. It may have at least one substituent selected from a linear, branched or cyclic alkoxy group or a phenyl group. ) R ¹ is a hydrogen atom,

The method for producing a triarylamine compound according to claim 14, wherein is a phenylene group fused to an adjacent 5-membered ring.

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