JP2019196323A - Method for producing 9-(1-naphthyl)-9h-carbazole derivative - Google Patents

Abstract

To provide a method for producing 9-(1-naphthyl)-9H-carbazole derivatives.SOLUTION: The production method includes causing a reaction to occur between a 9H-carbazole derivative and 1-halonaphthalene in the presence of a palladium compound, a biarylphosphine represented by formula (4), and a lithium base. (R: a C4-10 linear, branched or cyclic alkyl. Rand R: H or a benzene ring formed together with bonded C. R, R, R, Rand R: H, a C1-3 alkyl or the like).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a 9- (1-naphthyl) -9H-carbazole derivative.

  9H-carbazoles having a 1-naphthyl group at the 9-position are useful compounds as intermediates for producing hole transport materials for organic EL devices (for example, Patent Document 1). As a method for producing the compound using a palladium catalyst, 9H-carbazole and 1-bromonaphthalene are reacted in the presence of tris (dibenzylideneacetone) dipalladium, triphenylphosphine and sodium tert-butoxide, and 9- (1- A method for producing naphthyl) -9H-carbazole is disclosed in Patent Document 1, but it was unclear whether the described conditions were applicable to the production method of the present invention. Further, 4- (9H-carbazol-9-yl) -N- (alkyl or phenyl) -1,8-naphthalimide, which is one of 9- (1-naphthyl) -9H-carbazole derivatives, palladium acetate, Non-patent literature is a process for producing 9H-carbazole and 4-bromo-N- (alkyl or phenyl) -1,8-naphthalimide in the presence of tri (tert-butyl) phosphine and sodium tert-butoxide. 1 is disclosed. However, this is a method using a highly reactive halonaphthalene (4-bromo-N- (alkyl or phenyl) -1,8-naphthalimide) substituted with an electron withdrawing group as a substrate. It is unclear whether the above conditions are applicable to the production method of the present invention. On the other hand, 3-bromo-9H-carbazole in which a halogen atom is substituted on the carbon atom of 9H-carbazole and expensive 1-iodonaphthalene are reacted in the presence of tris (dibenzylideneacetone) dipalladium and tributylphosphine to produce 3 Although the method for producing -bromo-9- (1-naphthyl) -9H-carbazole is disclosed in Patent Document 2, it was unclear whether the described conditions were applicable to the production method of the present invention.

US Patent Application Publication No. 2015/0053942 US Patent Application Publication No. 2017/0162796

Dyes and Pigments, 2009, 80, 11 pages.

  Patent Document 1 describes a method for producing 9- (1-naphthyl) -9H-carbazole, but does not describe the yield. Although an attempt was made to produce 9- (1-naphthyl) -9H-carbazole from 9H-carbazole and 1-bromonaphthalene by this method, the target product was not confirmed (Comparative Example-1). Moreover, although the reaction of 9H-carbazole and 1-bromonaphthalene was tried using the palladium catalyst system of the nonpatent literature 1, the target object was not confirmed (comparative example-2). Furthermore, although the reaction of 9H-carbazole and 1-bromo or chloronaphthalene was also performed using a palladium compound or a base different from the method described in Non-Patent Document 1, the yield of the target product was low (comparative). Example 3-6). Although Patent Document 2 describes a method for producing 3-bromo-9- (1-naphthyl) -9H-carbazole, in this method, 9- (1-naphthyl) from 9H-carbazole and 1-bromonaphthalene is used. Although production of -9H-carbazole was attempted, the target product was not confirmed (Comparative Example-7).

  An object of the present invention is to efficiently produce a 9- (1-naphthyl) -9H-carbazole derivative from a 9H-carbazole derivative and 1-halonaphthalene in the presence of a palladium catalyst.

As a result of intensive investigations in view of the above problems, the present inventors have reacted 9H-carbazole derivatives and 1-halonaphthalene in the presence of a palladium compound, a phosphine compound and a base to produce 9- (1-naphthyl). ) In the method for producing a -9H-carbazole derivative, it was found that the target product can be produced efficiently by using biarylphosphine as the phosphine compound and lithium base as the base. That is, the present invention
(I) General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a halogen atom. P and q each independently represent 0, 1 or 2.)
A 9H-carbazole derivative represented by the general formula (2)

(In the formula, X represents a bromine atom or a chlorine atom.)
Is reacted with 1-halonaphthalene represented by general formula (3) in the presence of a palladium compound, a phosphine compound and a base.

(In the formula, R ¹ , R ² , p and q have the same contents as described above.)
In the method for producing a 9- (1-naphthyl) -9H-carbazole derivative represented by the formula:

(In the formula, each R ³ independently represents a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms. R ⁴ and R ⁵ are formed integrally with a hydrogen atom or carbon to be bonded. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or dimethylamino R ⁶ and R ⁷ may be combined with a carbon atom to be bonded to form a benzene ring, and R ⁶ , R ⁷ and R ⁸ may be combined with a carbon atom to be bonded. (A phenalene ring may be formed.)
A production method, wherein the base is a lithium base;
(Ii) The production method according to (i), wherein R ³ is a tert-butyl group, and R ⁴ and R ⁵ are hydrogen atoms;
(Iii) R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁶ is a dimethylamino group or a methyl group (i ) The production method described in;
(Iv) R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, and R ⁶ and R ¹⁰ are methoxy groups. Production method;
(V) R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁷ and R ⁹ are hydrogen atoms, and R ⁶ , R ⁸ and R ¹⁰ are isopropyl groups Production method;
(Vi) R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁶ , R ⁷ and R ⁸ are combined with the carbon atom to which they are bonded. The production method according to (i), which forms a phenalene ring;
(Vii) The production method according to any one of (i) to (vi), wherein the lithium base is lithium tert-butoxide, lithium bis (trimethylsilyl) amide or butyllithium.

  According to the present invention, a 9- (1-naphthyl) -9H-carbazole derivative, which is a compound useful as a raw material for a hole transport material for an organic EL device, is produced in one step more efficiently than the disclosed known method. be able to.

  The present invention is described in detail below.

  In the production method of the present invention, 9H- (1-naphthyl) is produced by reacting 9H-carbazole derivative (1) with 1-halonaphthalene (2) in the presence of a palladium compound, biarylphosphine (4) and a lithium base. This is a production method for obtaining a -9H-carbazole derivative (3).

Examples of the halogen atom represented by R ¹ and R ² of the 9H-carbazole derivative (1) that can be used in the production method of the present invention include an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom.

  The 9H-carbazole derivative (1) is not particularly limited, and examples thereof include 9H-carbazole, 2-chloro-9H-carbazole, 3-chloro-9H-carbazole, 4-chloro-9H-carbazole, 2- Bromo-9H-carbazole, 3-bromo-9H-carbazole, 4-bromo-9H-carbazole, 2-fluoro-9H-carbazole, 3-fluoro-9H-carbazole, 4-fluoro-9H-carbazole, 2-iodo- 9H-carbazole, 3-iodo-9H-carbazole, 4-iodo-9H-carbazole, 2,7-dichloro-9H-carbazole, 2,7-difluoro-9H-carbazole, 2,7-dibromo-9H-carbazole, 2-chloro-7-fluoro-9H-carbazole, 3-chloro-6-thio It can be exemplified Oro -9H- carbazole. Some of these 9H-carbazole derivatives (1) are commercially available. For example, Organic Letters, 20, 216, 2018, Green Chemistry, 20, 1362, 2018, Journal of Physical Chemistry C, 116, 20681 pages, 2012, Dies and Pigments, 132 pages, 1 page, 2016.

  The palladium compound that can be used in the present invention is not particularly limited. For example, zero-valent palladium compounds such as bis (dibenzylideneacetone) palladium and tris (dibenzylideneacetone) dipalladium, palladium chloride, bromide Examples thereof include divalent palladium compounds such as palladium, palladium acetate, π-allyl palladium chloride dimer, bis (acetylacetonato) palladium, dichlorobis (acetonitrile) palladium, and dichlorobis (benzonitrile) palladium. Among these, a zerovalent palladium compound is preferable in terms of a good yield, and tris (dibenzylideneacetone) dipalladium is more preferable.

  The amount of the palladium compound used is not particularly limited, but is preferably a so-called catalytic amount, specifically, 0.0001 equivalent to 0.5 equivalent is preferable with respect to the 9H-carbazole derivative (1). 0.01 equivalent to 0.25 equivalent is more preferable.

  Next, biarylphosphine (4) that can be used in the present invention will be described.

Although it does not specifically limit as a C4-C10 linear, branched or cyclic alkyl group shown by R < ³ >, Specifically, a butyl group, a tert- butyl group, a pentyl group, a hexyl group, Examples thereof include a cyclohexyl group and a 1-adamantyl group.

Specific examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, and an isopropyl group. .

Specific examples of the alkoxy group having 1 to 3 carbon atoms represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. it can.

  As the biarylphosphine (4) that can be used in the present invention, the following (A) to (AS) are preferable. Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, tBu represents a tert-butyl group, Ad represents a 1-adamantyl group, and Cy represents a cyclohexyl group.

  Of the above biarylphosphine (4), (A) to (AD) are more preferable in that the yield and selectivity of the target product are good, and 2-di (tert-butyl) phosphino-2′-dimethylamino- 1,1′-biphenyl (C), 2-di (tert-butyl) phosphino-2′-methyl-1,1′-biphenyl (E), 2-di (tert-butyl) phosphino-2,6-dimethoxy -1,1′-biphenyl (G), 2-di (tert-butyl) phosphino-2 ′, 4 ′, 6′-triisopropyl-1,1′-biphenyl (H), or 1- [2-di (Tert-Butyl) phosphinophenyl] pyrene (O) is particularly preferred.

  Although the usage-amount of biarylphosphine (4) is not specifically limited, 0.01 equivalent-10 equivalent are preferable with respect to a palladium compound, and 0.1 equivalent-5 equivalent are more preferable.

  A part of the biarylphosphine (4) that can be used in the present invention is commercially available, but can also be prepared according to, for example, Advanced Synthesis & Catalysis, 360, 1007, 2018.

  The lithium base that can be used in the present invention is not particularly limited. For example, lithium methoxide, lithium ethoxide, lithium isopropyl oxide, lithium tert-butoxide, lithium bis (trimethylsilyl) amide, lithium hydride, A butyl lithium etc. can be illustrated. From the viewpoint of good yield, lithium tert-butoxide, lithium bis (trimethylsilyl) amide or butyllithium is preferable.

  Although the usage-amount of a lithium base is not specifically limited, 0.1 equivalent-10 equivalent are preferable with respect to 9H-carbazole derivative (1), and 0.5 equivalent-5 equivalent are more preferable.

  The amount of 9H-carbazole derivative (1) used is preferably 0.1 equivalents to 10 equivalents, more preferably 0.5 equivalents to 5 equivalents, relative to 1-halonaphthalene (2).

  The production method of the present invention can be carried out in an organic solvent, and is preferably an organic solvent that does not adversely affect the reaction. The organic solvent is not particularly limited, but ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, 1,4-dioxane, methyl-tert-butyl ether, 1,2-dimethoxyethane, pentane, hexane. Examples thereof include aliphatic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as xylene, toluene, and benzene. Two or more of the above solvents may be mixed. In terms of good yield, aromatic hydrocarbon solvents are preferable, and xylene or toluene is more preferable.

  Although the manufacturing method of this invention is not specifically limited, It can implement at the temperature selected suitably from the temperature of 0 to 200 degreeC. 20 to 180 degreeC is preferable at a point with a good yield.

  As the reaction atmosphere, an inert gas such as argon or nitrogen gas is preferably used in terms of a good yield, but it may be in an air atmosphere.

  Although it is preferable to isolate the target product from the solution after the reaction, the isolation method is not particularly limited, but includes solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, General-purpose methods such as recrystallization or sublimation can be mentioned.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these. In addition, the liquid chromatography (HPLC) analysis as described in an Example was performed with the following method.
Column: ZORBAX Eclipse XDB-C18 (4.6 × 250 mm) manufactured by Agilent Technologies
Eluent: methanol / tetrahydrofuran = 9/1 (volume ratio)
Detector: UV / Vis detector (wavelength: 254 nm)
The HPLC yield of the target product by HPLC was calculated by the following method.
HPLC yield of target product: [number of moles of target product] / mol of charged 9H-carbazole derivative (1) calculated by internal standard method using 9- (p-tolyl) -9H-carbazole as internal standard substance number].

  Example-1

  Under an argon atmosphere, 167 mg (1.0 mmol) of 9H-carbazole, 4.6 mg (5.0 μmol) of tris (dibenzylideneacetone) dipalladium, and 2-di (tert-butyl) phosphino-2,6-dimethoxy were placed in a reaction vessel. −1,1′-biphenyl 12.5 mg (35 μmol) was suspended in xylene 5.0 mL, and 1.0 M-toluene solution of lithium bis (trimethylsilyl) amide (LiHMDS) 1.1 mL (1.1 mmol) and 1 -311 mg (1.5 mmol) of bromonaphthalene was added. The mixture was heated to 140 ° C. and stirred for 15 hours. After cooling to room temperature, 25 mL of water and 20 mL of ethyl acetate were added to the reaction mixture. An organic layer (0.1 mL) was collected, diluted with tetrahydrofuran (3.0 mL), and analyzed by HPLC to confirm that 95% of 9- (1-naphthyl) -9H-carbazole was produced.

The reaction mixture was extracted 3 times with 25 mL of ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dehydrated by adding anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 30/1 (volume ratio)), 9- (1-naphthyl) -9H-carbazole was obtained as a white solid (275 mg, 94%).
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 6.98-7.03 (2H, m), 7.26-7.37 (6H, m), 7.54 (1H, ddd, J = 1.5, 6.6, 8.2 Hz), 7.62-7.70 (2H, m), 8.02 (1H, d, J = 8.3 Hz), 8.03-8.07 ( 1H, m), 8.19-8.23 (2H, m). .

Example-2
The same operation as in Example 1 was carried out except that the amount of 1-bromonaphthalene used was 207 mg (1.0 mmol), and 9- (1-naphthyl) -9H-carbazole was found to be 9H-carbazole by HPLC analysis. It was confirmed that 78% was produced.

Example-3
In a reaction vessel, 167 mg (1.0 mmol) of 9H-carbazole, 4.6 mg (5.0 μmol) of tris (dibenzylideneacetone) dipalladium, 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1, After adding 12.5 mg (35 μmol) of 1′-biphenyl and 120 mg (1.5 mmol) of lithium-tert-butoxide, the inside of the reaction system was replaced with argon gas. After adding xylene (3.0 mL), 1-bromonaphthalene (207 mg, 1.0 mmol) was further added, and the mixture was heated to 140 ° C. and stirred for 15 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected and diluted with 3.0 mL of tetrahydrofuran, and then HPLC analysis showed that 9- (1-naphthyl) -9H-carbazole was 77% generated relative to the charged 9H-carbazole. confirmed.

Example-4
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2′-methyl-1,1′-biphenyl 11 The same operation as in Example 3 was performed except that 0.0 mg (35 μmol) was used, and by HPLC analysis, 9- (1-naphthyl) -9H-carbazole was 74% produced relative to the charged 9H-carbazole. I confirmed.

Example-5
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2 ′, 4 ′, 6′-triisopropyl- 9- (1-Naphtyl) -9H-carbazole was added to 9H-carbazole charged by HPLC analysis, except that 14.9 mg (35 μmol) of 1,1′-biphenyl was used. It was confirmed that 75% was produced.

Example-6
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 14.8 mg (35 μmol) of 1- [2-di (tert-butyl) phosphinophenyl] pyrene Except that was used, the same operation as in Example 3 was carried out, and it was confirmed by HPLC analysis that 9- (1-naphthyl) -9H-carbazole was formed to 78% of the charged 9H-carbazole. .

Example-7
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2′-dimethylamino-1,1′-biphenyl The same operation as in Example 3 was performed except that 12.0 mg (35 μmol) was used, and by HPLC analysis, 9- (1-naphthyl) -9H-carbazole was produced 59% with respect to the charged 9H-carbazole. Confirmed that.

Example-8
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-dicyclohexylphosphino-2 ′, 6′-bis (dimethylamino) -1,1 ′ -The same operation as Example-3 was carried out except using 15.3 mg (35 μmol) of biphenyl, and 9- (1-naphthyl) -9H-carbazole was found to be 40% based on 9H-carbazole charged by HPLC analysis. It was confirmed that it was generated.

  Example-9

  In a reaction vessel, 167 mg (1.0 mmol) of 9H-carbazole, 4.6 mg (5.0 μmol) of tris (dibenzylideneacetone) dipalladium, 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1, After adding 12.5 mg (35 μmol) of 1′-biphenyl and 120 mg (1.5 mmol) of lithium-tert-butoxide, the inside of the reaction system was replaced with argon gas. After adding 3.0 mL of xylene, 163 mg (1.0 mmol) of 1-chloronaphthalene was further added, heated to 140 ° C., and stirred for 15 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected, diluted with 3.0 mL of tetrahydrofuran, and analyzed by HPLC analysis to show that 95% of 9- (1-naphthyl) -9H-carbazole was produced relative to the charged 9H-carbazole. confirmed.

  The reaction mixture was extracted 3 times with 25 mL of ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dehydrated by adding anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 30/1 (volume ratio)), 9- (1-naphthyl) -9H-carbazole was obtained as a white solid (295 mg, 94%).

Example-10
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2′-methyl-1,1′-biphenyl 11 Except for using 0.0 mg (35 μmol), the same operation as in Example-9 was performed, and 9- (1-naphthyl) -9H-carbazole was found to be 91% produced with respect to 9H-carbazole charged by HPLC analysis. I confirmed.

Example-11
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2 ′, 4 ′, 6′-triisopropyl- 9- (1-Naphtyl) -9H-carbazole was added to 9H-carbazole charged by HPLC analysis, except that 14.9 mg (35 μmol) of 1,1′-biphenyl was used. It was confirmed that 72% was produced.

Example-12
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 14.8 mg (35 μmol) of 1- [2-di (tert-butyl) phosphinophenyl] pyrene Except that was used, the same operation as in Example-9 was performed, and it was confirmed by HPLC analysis that 9- (1-naphthyl) -9H-carbazole was produced in 80% with respect to the charged 9H-carbazole. .

Example-13
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-di (tert-butyl) phosphino-2′-dimethylamino-1,1′-biphenyl The same operation as in Example-9 was carried out except that 12.0 mg (35 μmol) was used, and HPLC analysis showed that 9- (1-naphthyl) -9H-carbazole was 77% produced relative to the charged 9H-carbazole. Confirmed that.

Example-14
Instead of 2-di (tert-butyl) phosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl, 2-dicyclohexylphosphino-2 ′, 6′-bis (dimethylamino) -1,1 ′ -The same operation as Example-9 was carried out except that 15.3 mg (35 µmol) of biphenyl was used, and HPLC analysis showed that 9- (1-naphthyl) -9H-carbazole was 38% with respect to 9H-carbazole charged. It was confirmed that it was generated.

  Example-15

  In a reaction vessel, 202 mg (1.0 mmol) of 2-chloro-9H-carbazole, 4.6 mg (5.0 μmol) of tris (dibenzylideneacetone) dipalladium, 2-di (tert-butyl) phosphino-2,6-dimethoxy- 1,1′-biphenyl 17.9 mg (0.05 mmol), lithium-tert-butoxide 120 mg (1.5 mmol), and 1-bromonaphthalene 311 mg (1.5 mmol) were added. After replacing the inside of the reaction system with argon gas, it was heated to 140 ° C. and stirred for 15 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected, diluted with 3.0 mL of tetrahydrofuran, and confirmed by HPLC analysis that 78% of 2-chloro-9- (1-naphthyl) -9H-carbazole was produced.

  The reaction mixture was extracted 3 times with 25 mL of ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dehydrated by adding anhydrous sodium sulfate, filtered, concentrated and purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 30/1 (volume ratio)) to give 2-chloro-9- ( 1-Naphthyl) -9H-carbazole was obtained as a white solid (229 mg, 70%).

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 6.95-7.00 (2H, m), 7.20-7.28 (2H, m), 7.28-7.38 (3H M), 7.55 (1H, ddd, J = 1.2, 6.9, 8.2 Hz), 7.62 (1H, dd, J = 1.3, 7.2 Hz), 7.68 ( 1H, dd, J = 7.7, 7.7 Hz), 8.03 (1H, d, J = 8.2 Hz), 8.07 (1H, d, J = 8.2 Hz), 8.10 (1H , D, J = 8.3 Hz), 8.14-8.18 (1H, m). .

Comparative Example-1
In a reaction vessel, 167 mg (1.0 mmol) of 9H-carbazole, 45.8 mg (0.05 mmol) of tris (dibenzylideneacetone) dipalladium, 26.2 mg (0.10 mmol) of triphenylphosphine, and 288 mg of sodium-tert-butoxide ( 3.0 mmol) was added, and the reaction system was replaced with argon gas. After adding 3.0 mL of toluene and further adding 228 mg (1.1 mmol) of 1-bromonaphthalene, the mixture was heated to 100 ° C. and stirred for 24 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected, diluted with 3.0 mL of tetrahydrofuran, and confirmed by HPLC analysis that 9- (1-naphthyl) -9H-carbazole was not generated.

Comparative Example-2
In a reaction vessel, 9H-carbazole 201 mg (1.2 mmol), palladium acetate 4.5 mg (0.02 mmol), tri-tert-butylphosphine 11.6 mg (0.04 mmol), and sodium-tert-butoxide 144 mg (1.5 mmol) ) And the inside of the reaction system was replaced with argon gas. After adding 3.0 mL of toluene and further adding 207 mg (1.0 mmol) of 1-bromonaphthalene, the mixture was heated to 120 ° C. and stirred for 15 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected, diluted with 3.0 mL of tetrahydrofuran, and confirmed by HPLC analysis that 9- (1-naphthyl) -9H-carbazole was not generated.

Comparative Example-3
In a reaction vessel, 167 g (1.0 mmol) of 9H-carbazole, 4.6 mg (5.0 μmol) of tris (dibenzylideneacetone) dipalladium, 7.1 mg (35 μmol) of tri-tert-butylphosphine, and 144 mg of sodium-tert-butoxide (1.5 mmol) was added, and the inside of the reaction system was replaced with argon gas. After adding 3.0 mL of toluene and further adding 207 mg (1.0 mmol) of 1-bromonaphthalene, the mixture was heated to 140 ° C. and stirred for 15 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. An ethyl acetate layer (0.1 mL) was collected, diluted with 3.0 mL of tetrahydrofuran, and confirmed by HPLC analysis that a trace amount of 9- (1-naphthyl) -9H-carbazole was formed.

Comparative Example-4
9- (1-naphthyl) -9H- was analyzed by HPLC analysis in the same manner as in Comparative Example-3 except that 120 mg (1.5 mmol) of lithium-tert-butoxide was used instead of sodium-tert-butoxide. It was confirmed that carbazole was produced 27% with respect to the charged 9H-carbazole.

Comparative Example-5
9- (1-naphthyl) -9H-carbazole was analyzed by HPLC analysis, except that 163 mg (1.0 mmol) of 1-chloronaphthalene was used instead of 1-bromonaphthalene, and HPLC analysis showed that It was confirmed that a trace amount was generated.

Comparative Example-6
The same as Comparative Example 3 except that 120 mg (1.5 mmol) of lithium-tert-butoxide was used instead of sodium-tert-butoxide, and 163 mg (1.0 mmol) of 1-chloronaphthalene was used instead of 1-bromonaphthalene. Operation was performed, and HPLC analysis confirmed that 24% of 9- (1-naphthyl) -9H-carbazole was produced.

Comparative Example-7
Under an argon atmosphere, 167 mg (1.0 mmol) of 9H-carbazole and 27.5 mg (30 μmol) of tris (dibenzylideneacetone) dipalladium were suspended in 10.0 mL of toluene in a reaction vessel. 12.1 mg (60 μmol) of tributylphosphine and 207 mg (1.0 mmol) of 1-bromonaphthalene were added thereto. The mixture was heated to 110 ° C. and stirred for 12 hours. After cooling to room temperature, 25 mL of water was added to stop the reaction. 20 mL of ethyl acetate was added and stirred until the ethyl acetate layer was uniform. 0.1 mL of an ethyl acetate layer was collected, diluted with 3.0 mL of tetrahydrofuran, and confirmed by HPLC analysis that 9- (1-naphthyl) -9H-carbazole was not generated.

Claims (7)

General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a halogen atom. P and q each independently represent 0, 1 or 2.)
A 9H-carbazole derivative represented by the general formula (2)

(In the formula, X represents a bromine atom or a chlorine atom.)
Is reacted with 1-halonaphthalene represented by general formula (3) in the presence of a palladium compound, a phosphine compound and a base.

(In the formula, R ¹ , R ² , p and q have the same contents as described above.)
In the method for producing a 9- (1-naphthyl) -9H-carbazole derivative represented by the formula:

(In the formula, each R ³ independently represents a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms. R ⁴ and R ⁵ are formed integrally with a hydrogen atom or bonded carbon. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or dimethyl R ⁶ and R ⁷ may be combined with a carbon atom to be bonded to form a benzene ring, and R ⁶ , R ⁷ and R ⁸ may be combined with a carbon atom to be bonded. To form a phenalene ring.)
A production method, wherein the base is a lithium base. The production method according to claim 1, wherein R ³ is a tert-butyl group, and R ⁴ and R ⁵ are hydrogen atoms. The R ³ is a tert-butyl group, the R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, and the R ⁶ is a dimethylamino group or a methyl group. Manufacturing method. The production method according to claim 1, wherein R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, and R ⁶ and R ¹⁰ are methoxy groups. The production method according to claim 1, wherein R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁷ and R ⁹ are hydrogen atoms, and R ⁶ , R ⁸ and R ¹⁰ are isopropyl groups. R ³ is a tert-butyl group, R ⁴ , R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁶ , R ⁷ and R ⁸ are combined with a carbon atom to form a phenalene ring. The manufacturing method of Claim 1 formed.   The production method according to any one of claims 1 to 6, wherein the lithium base is lithium tert-butoxide, lithium bis (trimethylsilyl) amide or butyllithium.