JP2018145113A - Method for producing triarylamines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method that makes it possible to obtain, conveniently and efficiently, triarylamines, useful as functional compounds for organic ELs, electrophotographic photoreceptors, organic semiconductors, solar cells or the like.SOLUTION: The present invention provides a method for producing triarylamines illustrated by (I-), including reacting diaryl amines and haloaryl compounds with Grignard reagents, to obtain magnesium diaryl amides and magnesium haloaryl compounds, before reacting it with transition metal catalysts.SELECTED DRAWING: None

Description

The present invention relates to triarylamines useful as functional compounds such as organic EL, electrophotographic photosensitive members, organic semiconductors, and solar cells, and more specifically to the production methods of (I) to (IV) below.
NH-free aromatic amino group-substituted anilines (I)
NH-free aromatic amino-substituted carbazoles (II)
OH-free aromatic amino group-substituted phenols (III)
SH-free aromatic amino group-substituted thiophenols (IV)

Triarylamines are useful as functional compounds such as organic EL, electrophotographic photoreceptors, organic semiconductors, solar cells, and many production methods have been reported.
As a method for producing NH-free aromatic amino group-substituted anilines (I), as shown in the following formula (i), a palladium compound and a phosphine ligand are used as a catalyst in the presence of a base from haloaniline compounds and diphenylamine compounds. A method for carrying out the arylamination reaction is generally used (see, for example, Patent Document 1).

  However, this method has a problem in that the free NH group of the haloaniline compound reacts with the haloaniline compound to generate a plurality of impurities that are difficult to separate from the target product, and the target product can be obtained only in a low yield. is there. Moreover, since expensive palladium and a phosphine ligand are used as a catalyst and expensive metal alkoxide is used as a base, it is not sufficient as an industrial production method.

On the other hand, Non-Patent Document 1 reports a method in which a free NH group of bromoaniline is protected and then reacted with a diphenylamine compound as shown in the following formula (ii). In this method, since the NH group is protected, generation of by-products that are difficult to separate can be suppressed.
However, this method has a problem of being multi-staged because it is necessary to protect and deprotect the NH group. Further, since expensive palladium and phosphine ligands are used as catalysts and expensive metal alkoxides are used as bases, they are not sufficient as industrial production methods.

  Patent Document 2 reports a method for producing NH-free aromatic amino group-substituted carbazoles (II). Similar to Non-Patent Document 1, this method has a problem of requiring multiple steps because it is necessary to protect and deprotect the free NH group of carbazole. Moreover, since expensive palladium and a phosphine ligand are used as a catalyst and expensive metal alkoxide is used as a base, it is not sufficient as an industrial production method.

  Non-Patent Document 2 and Patent Document 3 report methods for producing OH-free aromatic amino group-substituted phenols (III) and SH-free aromatic amino group-substituted thiophenols (IV), respectively. However, since expensive palladium or phosphine ligand is used as a catalyst and expensive metal alkoxide is used as a base, there is a problem that the cost is high, which is not sufficient as an industrial production method.

Japanese Patent No. 3161360 JP2015-193555A US Patent Application Publication No. 2016/0233428

Journal of Physical Chemistry C, Volume 115, Issue 30, 2011 (Year), 15008-15017 Journal of Polymer Science, Part A: Polymer Chemistry, Volume 50, Issue 18, 2012 (Year), pages 3788-3796.

  The objective of this invention is providing the manufacturing method which can obtain triarylamine useful as functional compounds, such as organic EL, an electrophotographic photoreceptor, an organic semiconductor, and a solar cell simply and efficiently.

As a result of studying the above problems, the present inventors reacted diarylamines and haloaryl compounds with Grignard reagents to obtain corresponding magnesium compounds, and then reacted transition metal catalysts with these magnesium compounds. As a result, it was found that triarylamines can be obtained easily and efficiently, and the present invention has been completed.
That is, the present invention provides the following general formula (1)

[In the formula (1), Ar ¹ , Ar ² and Ar ³ each independently represent an aryl group having a substituent or an unsubstituted aryl group, and Ar ² and Ar ³ may be condensed. A represents -NR, O, or S, and R represents a hydrogen atom, a substituted alkyl group having 1 to 30 carbon atoms, an unsubstituted alkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. Alternatively, it represents an aryl group having a substituent or an unsubstituted aryl group, and R and Ar ¹ may be condensed. ]
A process for producing a triarylamine represented by the formula:
The following general formula (2)

[In formula (2), Ar ² and Ar ³ are the same as those in formula (1), respectively. ]
And the following general formula (3)

[In Formula (3), X ¹ represents a halogen atom, and A and Ar ¹ are the same as those in Formula (1), respectively. ]
In the haloaryl compounds represented by
React with Grignard reagent,
The following general formula (4)

[In Formula (4), Ar ² and Ar ³ are the same as those in Formula (1), respectively, and X ² represents a halogen atom. ]
And a magnesium diarylamide represented by the following general formula (5)

[In the formula (5), A and Ar ¹ are the same as the formula (1), X ¹ is the same as the formula (3), and X ² is the same as the formula (4). ]
After obtaining the magnesium haloaryl compounds represented by
The present invention relates to a method for producing triarylamines, wherein a transition metal catalyst is reacted with magnesium diarylamides represented by the general formula (4) and magnesium haloaryl compounds represented by the general formula (5). Hereinafter, the present invention will be described in detail.

In the triarylamines represented by the general formula (1), in the formula (1), Ar ¹ , Ar ² and Ar ³ each independently represent an aryl group having a substituent or an unsubstituted aryl group, Ar ² and Ar ³ may be condensed. A represents -NR, O, or S, and R represents a hydrogen atom, a substituted alkyl group having 1 to 30 carbon atoms, an unsubstituted alkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. Alternatively, it represents an aryl group having a substituent or an unsubstituted aryl group, and R and Ar ¹ may be condensed.

  If a part of specific examples of the triarylamines represented by the general formula (1) are shown, the following compounds (1-1) to (1-63) may be mentioned.

  Moreover, if a part of specific example of diarylamines shown by the said General formula (2) is shown, the following compounds (2-1)-(2-13) can be mentioned.

In the haloaryl compounds represented by the general formula (3), in the formula (3),
X ¹ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
If a part of specific examples of the haloaryl compounds represented by the general formula (3) are shown, the following (3-1) to (3-21) may be mentioned.

In the magnesium diarylamides represented by the general formula (4), in the formula (4), X ² represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
<Method for producing triarylamines>
The triarylamines represented by the general formula (1) are not particularly limited, but can be produced by the following step 1 (magnesium compound preparation step) and step 2 (aryl amination step).

First, the magnesium compound preparation step, which is step 1, will be described.
In the present invention, the magnesium diarylamide represented by the general formula (4) can be produced by reacting the diarylamine represented by the general formula (2) with a Grignard reagent. Aryl compounds can be produced by reacting a haloaryl compound represented by the general formula (3) with a Grignard reagent.

  Therefore, in view of industrially producing the triarylamines represented by the general formula (1), the present inventors used Grignard reagents as diarylamines represented by the general formula (2) and the general formula (3). It is found that the magnesium diarylamides represented by the general formula (4) and the magnesium haloaryl compounds represented by the general formula (5) can be simultaneously produced by reacting with the arylaryl compounds represented by the formula It was found that the triarylamines represented by the general formula (1) can be obtained easily and efficiently.

  The Grignard reagent used in the present invention may be an aliphatic Grignard reagent or an aromatic Grignard reagent, such as methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium bromide, isopropyl magnesium chloride, butyl. Magnesium bromide, butyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride and the like are used.

  The amount of Grignard reagent used in the present invention is preferably 1.0 to 100 molar equivalents relative to the diarylamines represented by the general formula (2) or the haloaryl compounds represented by the general formula (3), More desirably, it is 1.1 molar equivalent to 10.0 molar equivalent. Grignard reagents may also be prepared from alkyl lithium and magnesium salts.

In the present invention, examples of the solvent used in the reaction include ether-based organic solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. Moreover, a solvent may be used individually or may be used in mixture of 2 or more types.
The amount of the solvent used is usually 1 part by weight to 1000 parts by weight with respect to 1 part by weight of the diarylamines represented by the general formula (2) or the haloaryl compounds represented by the general formula (3).

In the present invention, the reaction is desirably performed in an inert gas atmosphere such as nitrogen or argon, and can be performed under normal pressure or under pressure. The reaction temperature is preferably in the range of −50 ° C. to 300 ° C., but more preferably in the range of 0 ° C. to 150 ° C.
The reaction time varies depending on the type of substrate and the reaction temperature and is not particularly limited. However, the reaction can usually be completed within a range of 1 hour to 48 hours.

After completion of the reaction, the solvent may be removed under vacuum or normal pressure or may be used in the next step 2 as it is.
Next, the arylamination step as step 2 will be described.
The triarylamines represented by the general formula (1) are the above-described magnesium diarylamides (4) represented by the general formula (4) and magnesium haloaryl compounds represented by the general formula (5) (5). ) Can be produced by reacting a transition metal catalyst.

In this invention, the usage-amount of magnesium diarylamide (4) shown by General formula (4) is 1.0 molar equivalent-with respect to magnesium haloaryl compounds (5) shown by General formula (5). 10 molar equivalents are desirable, and more desirably 1.0 molar equivalents to 2.0 molar equivalents.
The transition metal catalyst used in the present invention may be an iron compound, a nickel compound, a copper compound or a cobalt compound.

  More specifically, for example, iron chlorides such as iron (II) chloride, iron (II) chloride tetrahydrate, iron (III) chloride, iron (III) chloride hexahydrate, and iron (II) bromide. , Iron bromide hydrate, Iron bromide (III), Iron bromide hydrate, etc., Iron fluoride (II), Iron fluoride (II) hydration , Iron fluoride such as iron (III) fluoride, iron fluoride (III) hydrate, iron iodide such as iron (II) iodide, iron (III) hydrate, iron acetate (II), iron (II) acetylacetonate, iron (III) acetylacetonate and other acetic acid-based iron organic compounds, iron (II) sulfate, hydrated iron (II) sulfate, iron (III) sulfate, Iron sulfates such as hydrates of iron (III) sulfate, nickel chlorides such as nickel (II) chloride and nickel (II) chloride hexahydrate, nickel (II) bromide, nickel (II) bromide Nickel bromides such as hydrates, nickel fluoride (II , Nickel fluoride such as nickel fluoride (II) hydrate, nickel iodide such as nickel iodide (II) and nickel iodide (II) hydrate, acetic acid such as nickel (II) acetylacetonate Nickel organic compounds, nickel sulfates such as nickel (II) sulfate and nickel (II) sulfate hydrates, copper chlorides such as copper (II) chloride and copper (II) chloride dihydrate, bromide Copper bromides such as copper (II), copper (II) bromide hydrates, copper fluorides such as copper fluoride (II) and copper fluoride (II) hydrates, copper iodide (II), Copper iodide such as copper iodide (II) hydrate, copper acetate (I), copper acetate (II), copper acetate (II) monohydrate, acetic acid such as copper (II) acetylacetonate Copper organic compounds, cobalt chlorides such as cobalt chloride (II) and cobalt chloride (II) hydrate, cobalt bromide (II), cobalt bromide (II) hydrate Cobalt fluoride such as cobalt bromide, cobalt fluoride (II), cobalt fluoride (II) hydrate, etc., cobalt iodide (II), cobalt iodide (II) hydrate, etc., Examples thereof include acetic acid-based cobalt organic compounds such as cobalt acetate (II), cobalt acetate (II) hexahydrate, and cobalt (II) acetylacetonate.

  Among these, in order to further improve the reaction yield, iron (II) chloride, iron (II) chloride tetrahydrate, iron (III) chloride, iron (III) chloride hexahydrate, iron bromide (II), Iron bromide (II) hydrate, Iron bromide (III), Iron bromide (III) hydrate, Iron fluoride (II), Iron fluoride (II) hydrate Iron halides such as iron (III) fluoride and iron (III) fluoride hydrate are more preferable, and iron chloride is particularly preferable.

The addition amount of the transition metal catalyst is preferably in the range of 0.01 mol% to 100 mol%, more preferably 0 to 1 mol of the magnesium diarylamides (4) or the magnesium haloaryl compounds (5). The range is from 0.05 mol% to 10.0 mol%.
In the present invention, the solvent used in the reaction may be either a polar solvent or a nonpolar solvent, such as aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, Mention may be made of ether organic solvents such as tertiary butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane. Moreover, a solvent may be used individually or may be used in mixture of 2 or more types.

The amount of the solvent used is usually 1 part by weight to 1000 parts by weight with respect to the magnesium diarylamides represented by the general formula (4) or the magnesium haloaryl compounds represented by the general formula (5).
The reaction is desirably performed in an inert gas atmosphere such as nitrogen or argon, and can be performed under normal pressure or under pressure. The reaction temperature is preferably in the range of 0 ° C to 300 ° C, more preferably in the range of 50 ° C to 200 ° C.

In the present invention, the reaction time varies depending on the type of substrate and the reaction temperature, and thus is not particularly limited, but the reaction can usually be completed within a range of 1 hour to 48 hours.
After completion of the reaction, generally known purification methods can be used. For example, water or dilute hydrochloric acid is added to the reaction solution to dissolve the generated salt, and then the organic layer is separated by a liquid separation operation. The obtained organic layer can be washed with water, brine, an alkaline aqueous solution or the like, and then isolated and purified by a general method such as column chromatography or crystallization.

  According to the present invention, triarylamines useful as functional compounds such as organic EL, electrophotographic photoreceptors, organic semiconductors, and solar cells can be obtained easily and efficiently.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, these Examples show the outline | summary of this invention and this invention is not limited to these Examples.
<Identification, quantification and analysis of compounds>
The target compound was identified by ¹ H NMR ( ¹ H nuclear magnetic resonance spectrum), ¹³ C NMR ( ¹³ C nuclear magnetic resonance spectrum), ¹⁹ F NMR ( ¹⁹ F nuclear magnetic resonance spectrum), MS (mass spectrometry spectrum), IR Determined by analysis, HRMS analysis, melting point analysis and elemental analysis. Purity was determined by GC analysis. The yield was determined by GC analysis using undecane as an internal standard. For purification of the target product, recycled preparative GPC was used as necessary.

The equipment used is as follows.
Nuclear magnetic resonance spectrum: JEOL ECS-400NR, Bruker AVANCE III 800US Plus
IR equipment: PerkinElmer Spectrum One FT-IR Spectrometer
HR-MS device: JEOL JMS-700 massspectrometer
Melting point measuring device: Yanaco MP-500D
GC device: Shimadzu GC-2010 (FID)
Column: ZB-1MS (10 m × 0.10 mm IDf: 0.1 μm) (Phenomenex)
Detector: Hydrogen flame ionization detector Recycle preparative GPC: Japan Analytical Industry LC-9204 instrument
Column: JAIGEL-1H-40 / JAIGEL-2H-40.

Example ^{1 (N 1, N 1 -di} -p-tolylbenzene-1,4-diamine (1-1))

  In a test tube (20 ml) with a screw-in type Teflon® stopper, di-p-tolylamine (118 mg, 0.598 mmol), 4-iodoaniline (65.2 mg, 0.298 mmol), diethyl ether (1.00 mL) After that, ethyl magnesium bromide in diethyl ether (300 μL, 3.00 M, 0.900 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Subsequently, iron (II) chloride tetrahydrate (3.00 mg, 15.1 μmol) and xylene (2.00 mL) were added, followed by aging at a heat block temperature of 140 ° C. for 24 hours. After cooling to room temperature, 1N hydrochloric acid (1.80 mL) was added to stop the reaction, and the mixture was neutralized with an aqueous sodium hydrogen carbonate solution. Extraction was performed using ethyl acetate (3.6 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

The obtained dried product was purified by silica gel column chromatography (hexane / ethyl acetate = 5/5) to obtain the target compound (1-1) as an off-white solid (yield: 93 %, Yield: 79.7 mg, purity: 97% (GC analysis)).
_{Anal, calcd for C 20 H 20} N 2 C, 83.30; H, 6.99; N, 9.71. found C, 83.22; H, 7.06; N, 9.42.

  Example 2

The same molar ratio and operation as in Example 1 were carried out except that the haloaryl compound was 4-bromoaniline, the reaction temperature of the arylamination step was changed to 160 ° C., and the aging time was changed to 36 hours.
The target compound (1-1) was obtained as an off-white solid (yield: 83%, yield: 71.6 mg, purity: 97% (GC analysis)).

Example ^{3 (N 1, N 1 -bis} (4-fluorophenyl) benzene-1,4-diamine (1-3))

  In a test tube (20 ml) with a screw-in type Teflon® stopper, bis (4-fluorophenyl) amine (124 mg, 0.604 mmol), 4-iodoaniline (65.6 mg, 0.300 mmol), diethyl ether (1 0.000 mL), ethyl diethyl bromide in diethyl ether (300 μL, 3.00 M, 0.900 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Subsequently, iron (II) chloride tetrahydrate (3.00 mg, 15.1 μmol) and xylene (2.00 mL) were added, followed by aging at a heat block temperature of 140 ° C. for 24 hours. After cooling to room temperature, 1N hydrochloric acid (1.80 mL) was added to stop the reaction, and the mixture was neutralized with an aqueous sodium hydrogen carbonate solution. Extraction was performed using ethyl acetate (3.6 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

The obtained dried product was purified by silica gel column chromatography (hexane / ethyl acetate = 5/5) and recycle preparative GPC to obtain the target compound (1-3) as an off-white solid. (Yield: 51%, yield: 45.6 mg, purity:> 99% (GC analysis)).
Mp: 108.0-109.0 ° C
IR (neat, cm ⁻¹ ) 3470, 3370, 1623, 1496, 1266, 1216, 1154, 1095, 824, 808
¹ H NMR (CDCl ₃ , 392 MHz) δ 3.63 (s, 2H), 6.63 (d, J = 8.6 Hz, 2H), 6.87-6.96 (m, 10H)
_{^{13 C NMR (CDCl 3, 98.5MHz}} ) δ115.9 (d, J c-f = 22Hz), 116.3,124.1 (d, J c-f = 7.5Hz), 127.1,139 _{.3,143.0,144.8,158.2 (d, J c-f} = 242Hz)
¹⁹ F NMR (CDCl ₃ , 368 MHz) δ-122.3
_{^{HRMS (EI) m / z [}} M] + calc for C 18 H 14 F 2 N 2 296.1125; found 296.1123.

  Example 4 (4- (di-p-tolylamino) phenol (1-40))

  In a test tube (20 ml) with a screw-in Teflon (registered trademark) stopper, di-p-tolylamine (118 mg, 0.598 mmol), 4-bromophenol (51.8 mg, 0.299 mmol), diethyl ether (1.00 mL) After that, ethyl magnesium bromide in diethyl ether (300 μL, 3.00 M, 0.900 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain a magnesium amide body and a magnesium phenoxide body.

  Subsequently, iron (II) chloride tetrahydrate (3.00 mg, 15.1 μmol) and xylene (2.00 mL) were added, followed by aging at a heat block temperature of 160 ° C. for 24 hours. After cooling to room temperature, 1N hydrochloric acid (1.80 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (3.6 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

The obtained dried product was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain the target compound (1-40) as a purple solid (yield: 76%, Yield: 66.5 mg, purity:> 99% (GC analysis)).
HRMS (EI) m / z [M] ⁺ calcd for C ₂₀ H ₁₉ NO 289.1467. found 2899.1466.

  Example 5 (N, N-diphenyl-1H-indol-5-amine (1-14))

  After charging test tube (20 ml) with screw-in Teflon (registered trademark) with diphenylamine (101 mg, 0.597 mmol), 5-bromoindole (59.3 mg, 0.302 mmol) and diethyl ether (1.00 mL) A diethyl ether solution of ethyl magnesium bromide (300 μL, 3.00 M, 0.900 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Subsequently, iron (II) chloride tetrahydrate (3.00 mg, 15.1 μmol) and xylene (2.00 mL) were added, followed by aging at a heat block temperature of 160 ° C. for 24 hours. After cooling to room temperature, 1N hydrochloric acid (1.80 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (3.6 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

The obtained dried product was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain the target compound (1-14) as a yellow solid (yield: 76%, Yield: 65.0 mg, purity: 96% (GC analysis)).
Mp: 118.5-119.6 ° C
IR (neat, cm ⁻¹ ) 3401, 3059, 1582, 1491, 1472, 1452, 1417, 1337, 1283, 1255, 1169, 1142, 1023, 894, 884, 867, 855, 802, 752, 730, 708, 694,654,608,581
¹ H NMR (CDCl ₃ , 392 MHz) δ 6.89-6.93 (m, 2H), 7.03 (dd, J = 2.4, 7.1 Hz, 1H), 7.06 (m, 4H), 7.17-7.21 (m, 5H), 7.32 (d, J = 7.8 Hz, 2H), 7.42 (m, 1H), 8.08 (s, 1H)
¹³ C NMR (CDCl ₃ , 98.5 MHz) δ 102.9, 112.0, 119.1, 121.5, 122.5, 122.8, 125.1, 128.9, 129.1, 133.4 , 140.6, 148.9
_{Anal, calcd for C 20 H 16} N 2 C, 84.48; H, 5.67; N, 9.85. found C, 84.40; H, 5.85; N, 9.70.

  Example 6 (N, N-di-p-tolyl-9H-carbazole-3-amine (1-25))

  In a test tube (20 ml) with a screw-type Teflon (registered trademark) stopper, di-p-tolylamine (59.0 mg, 0.299 mmol), 3-iodo-9H-carbazole (87.8 mg, 0.300 mmol), diethyl ether (1.50 mL) was added, and a diethyl ether solution of ethyl magnesium bromide (200 μL, 3.00 M, 0.600 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Next, iron (II) chloride tetrahydrate (3.10 mg, 15.6 μmol) and toluene (2.00 mL) were added, followed by aging at a heat block temperature of 80 ° C. for 6 hours. After cooling to room temperature, 1N hydrochloric acid (1.20 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.4 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

The obtained dried product was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain the target compound (1-25) as a white solid (yield: 93%, Yield: 101 mg, purity: 97% (GC analysis)).
Mp: 228.5-229.5 ° C
IR (neat, cm ⁻¹ ) 3421, 3386, 3028, 2918, 1606, 1505, 1490, 1475, 1460, 1322, 1310, 1233, 1177, 1110, 812
¹ H NMR (DMSO-d ₆ , 392 Hz) δ 2.28 (s, 6H), 6.91 (m, 4H), 7.08 (m, 4H), 7.12 (dd, J = 0.8, 7.8 Hz, 1 H), 7.16 (dd, J = 2.0, 7.8 Hz, 1 H), 7.40 (td, J = 1.1, 7.8 Hz, 1 H), 7.50 (d , J = 8.6 Hz, 1H), 7.51 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 2.0 Hz, 1H), 8.05 (d, J = 7. 8Hz, 1H), 11.3 (s, 1H)
¹³ C NMR (DMSO-d ₆ , 98.5 Hz) δ 20.23, 111.0, 112.0, 118.0, 118.4, 120.3, 122.0, 122.1, 123.3, 125 0.0, 125.6, 129.6, 130.1, 136.9, 139.0, 140.3, 146.1
HRMS (EI) m / z [M] ⁺ calcd for C ₂₆ H ₂₂ N ₂ 362.1783. found 362.1782.

Example 7
It implemented by the same molar ratio and operation as Example 6 except having changed the iron compound into anhydrous iron (III) chloride.
The target compound (1-25) was obtained as a white solid (yield: 85%, yield: 92.3 mg, purity: 98% (GC analysis)).

Example 8
It implemented by the same molar ratio and operation as Example 6 except having changed the iron compound into iron (III) chloride hexahydrate. When quantification was performed by GC analysis at 6 hours of aging, the yield of the target compound (1-25) was 26%.
Example 9
The same molar ratio and operation as in Example 6 were performed except that the iron compound was anhydrous iron (II) chloride, the solvent was changed to xylene, and the heat block temperature was 140 ° C. When quantification was performed by GC analysis at 6 hours of aging, the yield of the target compound (1-25) was 87%.

Example 10
The same molar ratio and operation as in Example 6 were performed except that the haloaryl compound was 3-bromo-9H-carbazole and the heat block temperature was changed to 120 ° C. As a result of GC analysis at 6 hours of aging, the yield of the target compound (1-25) was 78%.

Example 11
It implemented by the same molar ratio and operation as Example 7 except having changed the solvent into tetrahydrofuran. When quantification was performed by GC analysis at 6 hours of aging, the yield of the target compound (1-25) was 10%.
Example 12
The same molar ratio and operation as in Example 6 were carried out except that the catalyst was changed to nickel (II) chloride hexahydrate. When quantification was performed by GC analysis at 6 hours of aging, the yield of the target compound (1-25) was 59%.

Example ^{13 (N 3, N 3,} N 6, N 6 -tetra-p-tolyl-9H-carbazole-3,6-diamine (1-37))

  In a test tube (20 ml) with a screw-in type Teflon® stopper, di-p-tolylamine (59.3 mg, 0.301 mmol), 3,6-diiodocarbazole (62.6 mg, 0.149 mmol), diethyl ether (1.50 mL) was added, and then an ethyl magnesium bromide diethyl ether solution (150 μL, 3.00 M, 0.450 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Subsequently, iron (II) chloride tetrahydrate (1.50 mg, 7.56 μmol) and toluene (2.00 mL) were added, followed by aging at a heat block temperature of 100 ° C. for 6 hours. After cooling to room temperature, 1N hydrochloric acid (0.900 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (1.8 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

Of the obtained 96.6 mg of the dried solid product, 91.3 mg was purified by recycle preparative GPC to obtain the target compound (1-37) as a white solid (yield: 62%, yield). : 48.9 mg, purity: 96% (GC analysis)).
Example ^{14 (N 3, N 3,} N 6, N 6 -tetra-p-tolyl-9H-carbazole-3,6-diamine (1-37))

  A test tube (20 ml) with a screw-in type Teflon® stopper was charged with di-p-tolylamine (59.5 mg, 0.302 mmol), 3,6-dibromocarbazole (48.5 mg, 0.149 mmol), diethyl ether ( 1.50 mL) was added, and then an ethyl magnesium bromide diethyl ether solution (150 μL, 3.00 M, 0.450 mmol) was added dropwise at an internal temperature of 25 ° C. Then, after stirring for 10 minutes at a heat block temperature of 25 ° C., the solvent was removed to obtain respective magnesium amide compounds.

  Next, iron (II) chloride tetrahydrate (1.50 mg, 7.56 μmol) and xylene (2.00 mL) were added, followed by aging at a heat block temperature of 140 ° C. for 6 hours. After cooling to room temperature, 1N hydrochloric acid (0.900 mL) was added to stop the reaction, and neutralized with an aqueous sodium hydrogen carbonate solution. Extraction was performed using ethyl acetate (1.8 mL × 4 times), and the obtained organic layer was filtered using Florisil and then concentrated to dryness.

91.9 mg of the obtained dried product 96.5 mg was purified by recycle preparative GPC to obtain the target compound (1-37) as a white solid (yield: 41%, yield). : 32.9 mg, purity:> 99% (GC analysis)).
Mp: 153.0-154.2 ° C
IR (neat, cm ⁻¹ ) 3401, 3022, 2917, 1605, 1505, 1487, 1460, 1319, 1272, 1229, 807
¹ H NMR (DMSO-d ₆ , 392 MHz) δ 2.21 (s, 12H), 6.82 (m, 8H), 7.00 (m, 8H) 7.10 (dd, J = 2.0, 8 .6 Hz, 2H) 7.44 (d, J = 9.0 Hz, 2H), 7.74 (d, J = 2.0 Hz, 2H), 11.2 (s, 1H)
¹³ C NMR (DMSO-d ₆ , 98.5 MHz) δ 20.22, 112.1, 118.3, 121.9, 123.2, 125.4, 129.6, 130.1, 137.5, 138 .9, 146.0
HRMS (EI) m / z [M] ⁺ calcd for C ₄₀ H ₃₅ N ₃ 557.2831; found 557.2832
Comparative Example 1

In a test tube (20 ml) with a screw-in type Teflon® stopper, di-p-tolylamine (59.9 mg, 0.304 mmol), 3-iodo-9H-carbazole (88.5 mg, 0.302 mmol) under an argon atmosphere. ), Palladium acetate (3.26 mg, 14.5 μmol, 5 mol%), tri-tert-butylphosphine (11.5 mg, 56.8 μmol, 20 mol%), sodium tert-butoxide (33.9 mg, 0.353 mmol), Xylene (2 mL) was charged. Next, aging was performed at a heat block temperature of 160 ° C. for 1 hour.
When the quantitative analysis by GC analysis was performed, the yield of the target compound (1-25) was 0%.

Comparative Example 2
It implemented by the same molar ratio and operation as the comparative example 1 except having made the haloaryl compound into 4-bromo-9H-carbazole and changing the heat block temperature into 140 degreeC.
When quantification was performed by GC analysis during 1 hour of aging, the yield of the target compound (1-25) was 2%.

  Comparative Example 3

  In a test tube (20 ml) with a screw-in Teflon® stopper, di-p-tolylamine (60.3 mg, 0.306 mmol), 3-iodo-9H-carbazole (87.0 mg, 0.297 mmol) under an argon atmosphere. ), Anhydrous copper (I) chloride (1.08 mg, 10.9 μmol, 3.5 mol%), 1,10-phenanthroline (2.40 mg, 13.3 μmol, 3.5 mol%), potassium hydroxide (131 mg, 2 mol .34 mmol) and xylene (2.0 mL) were charged. Next, aging was performed at a heat block temperature of 160 ° C. for 1 hour.

When the quantitative analysis by GC analysis was performed, the yield of the target compound (1-25) was 0%.
The above Examples 1-17 and Comparative Examples 1-3 were summarized as Table 1 and Table 2, respectively.

Claims (2)

The following general formula (1)

[In the formula (1), Ar ¹ , Ar ² and Ar ³ each independently represent an aryl group having a substituent or an unsubstituted aryl group, and Ar ² and Ar ³ may be condensed. A represents -NR, O, or S, and R represents a hydrogen atom, a substituted alkyl group having 1 to 30 carbon atoms, an unsubstituted alkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. Alternatively, it represents an aryl group having a substituent or an unsubstituted aryl group, and R and Ar ¹ may be condensed. ]
A process for producing a triarylamine represented by the formula:
The following general formula (2)

[In formula (2), Ar ² and Ar ³ are the same as those in formula (1), respectively. ]
And the following general formula (3)

[In Formula (3), X ¹ represents a halogen atom, and A and Ar ¹ are the same as those in Formula (1), respectively. ]
In the haloaryl compounds represented by
React with Grignard reagent,
The following general formula (4)

[In Formula (4), Ar ² and Ar ³ are the same as those in Formula (1), respectively, and X ² represents a halogen atom. ]
Magnesium diarylamides (4) represented by the following general formula (5)

[In the formula (5), A and Ar ¹ are the same as the formula (1), X ¹ is the same as the formula (3), and X ² is the same as the formula (4). ]
After obtaining the magnesium haloaryl compounds represented by
A method for producing triarylamines, comprising reacting a magnesium diarylamide represented by the general formula (4) and a magnesium haloaryl compound represented by the general formula (5) with a transition metal catalyst. The method for producing a triarylamine according to claim 1, wherein the transition metal catalyst is an iron compound.