KR20090088177A - Polyaromatic compounds possessing naphthyl groups and process for preparing them - Google Patents

Abstract

A method for manufacturing an aromatic multicyclic compound is provided to synthesize the aromatic multicyclic compound with excellent yield by intersection-pairing reaction with various electrophilic aromatic compounds by in-situ reaction. An aromatic multicyclic compound has a naphthyl group represented by chemical formula 1. In chemical formula 1, A is an aromatic multicyclic group selected from 1,1'-biphenyl, 4- iodo-1,1'-biphenyl, 4-bromo-1,1'-biphenyl, 9,10-anthracenyl, fluorenyl, 9,9'-dimethylfluorenyl, carbazolyl, 9-ethylcarbazolyl, 2,2'-bithiophenyl, 9,9'-spirobifluorenyl and 1-pyrenyl.

Description

Aromatic polycyclic compounds having naphthyl groups and methods for preparing the compounds {Polyaromatic compounds possessing naphthyl groups and process for preparing them}

The present invention relates to an aromatic polycyclic compound having a naphthyl group and a method for preparing the compound. More particularly, after a naphthyl lithium is reacted with indium chloride (InCl ₃ ) to prepare a naphthyl indium reagent, a transition metal catalyst The present invention relates to an aromatic polycyclic compound having a naphthyl group represented by the following Chemical Formula 1 of a novel structure prepared by cross-pairing with an aromatic polycyclic compound having an electrophilic group, and a method for preparing the same.

[Formula 1]

는 1,1'-바이페닐, 4-요오도-1,1'-바이페닐, 4-브로모-1,1'-바이페닐, 9,10-안트라센일, 플루오렌일, 9,9'-디메틸플루오렌일, 카바졸일, 9-에틸카바졸일, 2,2'-바이티오펜일, 9,9'-스파이로바이플루오렌일, 및 1-파이렌일 중 에서 선택된 방향족 다중 고리기이고, 상기 친전자성 그룹을 갖는 방향족 다중 고리는 할로겐, C₁-C₆ 알킬설포네이트, 페닐설포네이트, 4-트리플루오로메틸페닐설포네이트, 트리플루오로메탄설포네이트, 및 디아조늄염 [N₂Y(이때, Y는 Cl, Br, I)] 중에서 선택된 치환체로 치환 또는 비치환될 수 있고; n은 1 또는 2의 정수이다.In Chemical Formula 1,

Is 1,1'-biphenyl, 4-iodo-1,1'-biphenyl, 4-bromo-1,1'-biphenyl, 9,10-anthracenyl, fluorenyl, 9,9 ' Aromatic cyclic group selected from -dimethylfluorenyl, carbazolyl, 9-ethylcarbazolyl, 2,2'-bithiophenyl, 9,9'-spirobifluorenyl, and 1-pyrenyl , The aromatic multi-ring having the electrophilic group is halogen, C ₁ -C ₆ alkylsulfonate, phenylsulfonate, 4-trifluoromethylphenylsulfonate, trifluoromethanesulfonate, and diazonium salt [N ₂ Y (where Y is Cl, Br, I)] may be substituted or unsubstituted; n is an integer of 1 or 2.

Cross-coupling reactions using metal catalysts to form carbon-carbon bonds are currently recognized as the most effective reactions in the field of organic chemistry. Organometallic compounds such as boron (B), magnesium (Mg), tin (Sn), zinc (Zn), and silicon (Si) are commonly used in the cross-coupling reaction. Efforts to make unsaturated, conjugated aromatic polycyclic compounds using such cross-coupling reactions have attracted much attention due to the inherent properties of aromatic polycyclic compounds.

This interest has primarily used methods of synthesizing by reacting organomagnesium reagents, organoboron reagents or organotin reagents with aromatic halides under transition metal catalyst conditions. Recently, research on cross-coupling reactions using organoindium reagents under palladium catalysis has been introduced, and advantages over previous synthesis have begun to emerge. J. Am. Chem. Soc . 1992 , 114 , 1018; J. Am. Chem. Soc . 1994 , 116 , 4537; Chem. rev . 1996 , 96 , 537; Organic. Lett. 1999 , 1 , 1027; Angew. Chem., Int. Ed . 2000 , 39 , 3140; Organic. Lett. 2001 , 3 , 2419; Organic. Lett. 1999 , 1 , 1267; J. Am. Chem. Soc . 2001 , 123 , 4155; Chem. Comm . 2002 , 2246; Synthesis 2003 , 780; Synthesis 2005 , 485]

However, any document reported to date has synthesized an aromatic polycyclic compound having a naphthyl group by cross-coupling reaction of a naphthyl indium reagent with an aromatic polycyclic compound having an electrophilic group in the presence of a transition metal catalyst. There is no bar.

The present invention has an object to provide an aromatic polycyclic compound having a naphthyl group having a novel structure represented by the formula (1).

In addition, the present invention is a method for efficiently preparing an aromatic polycyclic compound having a naphthyl group represented by the formula (1) by the cross-coupling reaction between the organic naphthyl indium reagent and the electrophilic aromatic polycyclic compound of various structures There is another purpose to provide.

The present invention is characterized by an aromatic polycyclic compound having a naphthyl group represented by the following formula (1) and a method for preparing the same.

[Formula 1]

는 1,1'-바이페닐, 4-요오도-1,1'-바이페닐, 4-브로모-1,1'-바이페닐, 9,10-안트라센일, 플루오렌일, 9,9'-디메틸플루오렌일, 카바졸일, 9-에틸카바졸일, 2,2'-바이티오펜일, 9,9'-스파이로바이플루오렌일, 및 1-파이렌일 중에서 선택된 방향족 다중 고리기이고, 상기 친전자성 그룹을 갖는 방향족 다중 고리는 할로겐, C₁-C₆ 알킬설포네이트, 페닐설포네이트, 4-트리플루오로메틸페닐설포네이트, 트리플루오로메탄설포네이트, 및 디아조늄염 [N₂Y(이때, Y는 Cl, Br, I)] 중에서 선택된 치환체로 치환 또는 비치환될 수 있고; n은 1 또는 2의 정수이다.In Chemical Formula 1,

Is 1,1'-biphenyl, 4-iodo-1,1'-biphenyl, 4-bromo-1,1'-biphenyl, 9,10-anthracenyl, fluorenyl, 9,9 ' -Dimethyl fluorenyl, carbazolyl, 9-ethylcarbazolyl, 2,2'-bithiophenyl, 9,9'-spirobifluorenyl, and 1-pyrenyl, Aromatic multiple rings with electrophilic groups include halogens, C ₁ -C ₆ alkylsulfonates, phenylsulfonates, 4-trifluoromethylphenylsulfonates, trifluoromethanesulfonates, and diazonium salts [N ₂ Y Wherein Y may be substituted or unsubstituted with a substituent selected from: Cl, Br, I); n is an integer of 1 or 2.

Specific examples of the aromatic polycyclic compound having a naphthyl group represented by Formula 1 according to the present invention are as follows:

4,4'-bis (1-naphthyl) -1,1'-biphenyl,

9,10-di (1-naphthyl) -anthracene,

2,7-di (1-naphthyl) -9,9'-dimethylfluorene,

3,6-di (1-naphthyl) -9-ethylcarbazole,

5,5'-bis (1-naphthyl) -2,2'-bithiophene,

2- (1-naphthyl) -9,9'-spirobifluorene,

1- (1-naphthyl) -pyrene,

2- (4'-iodo [1,1'-biphenyl] -4-yl) -naphthalene

2- (4'-Bromo [1,1'-biphenyl] -4-yl) -naphthalene

9,10-di- (2-naphthyl) -anthracene,

2,7-di (2-naphthyl) -9,9'-dimethylfluorene,

3,6-di (2-naphthyl) -9-ethylcarbazole,

2- (2-naphthyl) -9,9'-spirobifluorene,

1- (2-naphthyl) -pyrene.

Method for producing an aromatic multi-ring compound having a naphthyl group represented by the formula (1) according to the present invention comprises a two-step manufacturing process as follows.

The first process is to prepare a naphthyl halide represented by the following formula (2) with butyllithium to produce naphthyl lithium, and then react with indium chloride (InCl ₃ ) to prepare a naphthyl indium reagent represented by the following formula ( ₃ ) to be. That is, after the 1- or 2-naphthyl halide represented by the formula (2) is converted to 1- or 2-naphthyl lithium by reaction with butyllithium (n-BuLi or t-BuLi), indium chloride (InCl ₃ ) It is a process for preparing an organic naphthyl indium reagent represented by the following formula (3).

In the above scheme, X is a halogen atom.

In the second process, the naphthyl indium reagent represented by the following formula (3) is cross-coupled with the aromatic polycyclic compound represented by the following formula (4) in the presence of a transition metal catalyst to produce an aromatic multiple ring having a naphthyl group as the present invention. The process of preparing the compound.

In the above scheme, X is hydrogen atom, halogen atom, C ₁ -C ₆ alkylsulfonate, phenylsulfonate, 4-trifluoromethylphenylsulfonate, trifluoromethanesulfonate, and diazonium salt [N ₂ Y ( In this case, Y is Cl, Br, I)] n substituents selected from, except when the substituents (X) are all hydrogen atoms, n is an integer of 1 or 2.

In the preparation method according to the present invention, after synthesizing the naphthyl indium reagent represented by the formula (3) from the naphthyl halide represented by the formula (2), the naphthyl indium reagent is in-situ (in situ) without a separate separation and purification process Also included as a right to perform a cross-pairing reaction with the aromatic multi-ring compound represented by the formula (4).

In the present invention, 'in situ' refers to performing a cross-pairing reaction with an electrophile represented by Chemical Formula 4 without separately separating and purifying the naphthyl indium reagent represented by Chemical Formula 3. It means a manufacturing method.

The reaction solvent used in the production method of the present invention is a conventional organic solvent can be used, for example, the emitter (Et ₂ O), tetrahydrofuran (THF), 1,4- dioxane, diethylether. Preferably it is carried out using tetrahydrofuran (THF).

Hereinafter, the first process of preparing the naphthyl indium reagent represented by Chemical Formula 3 will be described in detail. Naphthyl halide represented by Chemical Formula 2 is prepared by using 1 to 1.5 equivalents for n-BuLi and 1.6 to 2.1 equivalents for t-BuLi in an Et ₂ O solvent. Trinaphthyl indium was then prepared by reacting naphthyllithium with indium chloride at -90 ° C to -50 ° C and THF solvent. At this time, it is economical to use a 3.0 molar ratio of naphthyl lithium based on 1.0 mole of indium chloride (InCl ₃ ), but it is preferable to use a slight excess amount of indium chloride to naphthyl lithium in terms of yield.

Hereinafter, a second process of preparing an aromatic polycyclic compound having a naphthyl group represented by Chemical Formula 1 will be described in detail. In the present invention, an aromatic polycyclic compound represented by Chemical Formula 4 is used as an electrophile used in the cross-pairing reaction, and specific examples of the aromatic polycyclic compound are as follows.

In the electrophile, R ₁ and R ₂ each represent a hydrogen atom or a C ₁ -C ₆ alkyl group; X ₁ and X ₂ each represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkylsulfonate group, a phenylsulfonate group, a 4-trifluoromethylphenylsulfonate group, a trifluoromethane-sulfonate group, and a diazo Nium salt [N ₂ Y (where Y is Cl, Br, I)] is selected, except when both X ₁ and X ₂ are hydrogen atoms at the same time.

부분을 구성하는 방향족 다중 고리기는 구체적으로 1,1'-바이페닐, 4-요오도-1,1'-바이페닐, 4-브로모-1,1'-바이페닐, 9,10-안트라센일, 플루오렌일, 9,9'-디메틸플루오렌일, 카바졸일, 9-에틸카바졸일, 2,2'-바이티오펜일, 9,9'-스파이로바이플루오렌일, 및 1-파이렌일 등이 포함될 수 있다.In the chemical structure of an aromatic polycyclic compound having a naphthyl group represented by Formula 1 according to the present invention,

The aromatic polycyclic group constituting the moiety is specifically 1,1'-biphenyl, 4-iodo-1,1'-biphenyl, 4-bromo-1,1'-biphenyl, 9,10-anthracenyl , Fluorenyl, 9,9'-dimethylfluorenyl, carbazolyl, 9-ethylcarbazolyl, 2,2'-bithiophenyl, 9,9'-spirobifluorenyl, and 1-pi Silane and the like.

The cross-coupling reaction temperature of the present invention is in the range of 30 ° C. to 90 ° C., preferably 60 ° C. to 75 ° C., particularly preferably to maintain reflux conditions using a tetrahydrofuran solvent. .

The naphthyl indium reagent represented by Chemical Formula 3 used in the cross-coupling reaction is used in the range of 0.5 to 2.0 equivalents with respect to the aromatic polycyclic compound represented by Chemical Formula 4.

In addition, the cross-coupling reaction of the present invention is carried out under a transition metal catalyst, specifically, a transition metal-containing compound such as palladium or nickel may be used as the transition metal catalyst. For example, as the palladium-containing compound, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) [(dppf) PdCl ₂ ], tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ], dichlorobis (triphenylphosphine) palladium (II) [(PPh ₃ ) ₂ PdCl ₂ ], dichloro [bis (2-diphenylphosphinophenyl) ethyl] palladium (II) [(DPEphos) PdCl ₂ ] _, palladium (II) chloride [PdCl ₂ ], palladium (II) acetoside [Pd (OAc) ₂ ], and bis (acetonitrile) dichloropalladium (II) [Pd (CH ₃ CN) ₂ Cl ₂ ] May be used. As the transition metal catalyst, tetrakis (triphenylphosphane) palladium (0) [Pd (PPh ₃ ) ₄ ] is unstable at room temperature, so palladium tris (dibenzylideneaceto) chloroform [Pd ₂ dba ₃ CHCl ₃ ] and triphenylphosphine [PPh ₃ ] may be used directly as a product obtained by reacting. Although the palladium compound is used as the transition metal catalyst in the embodiment of the present invention, the object of the present invention can be easily achieved even if the reaction is performed under the other transition metal catalysts exemplified above.

As the reaction conditions for carrying out the preparation method of the present invention as described above, the reaction time may vary depending on the reactants, the type of solvent, and the amount of the solvent. Make it complete. After the reaction is completed, the solvent may be distilled off under reduced pressure through an extraction process, and then the target product may be separated and purified through a conventional method such as column chromatography or recrystallization.

The present invention as described above will be described in more detail with reference to the following examples, the following examples are intended to help the understanding of the present invention is not limited to the scope of the present invention.

Preparation Example Preparation of Organic Indium Reagent

Preparation Example 1. Preparation of tri (1-naphthyl) indium reagent.

Add 2 mL of Et ₂ O to a 25 mL flask, adjust to -78 ° C, add t- BuLi (1.7M in pentane, 1.08 mL, 1.83 mmol), add 1-bromonaphthalene (128.02 μL, 0.915 mmol), and then- Stir at 78 ° C. for 15 minutes. After 15 minutes, it was raised to room temperature to prepare 1-naphthyl lithium.

In another 25 mL flask, InCl ₃ (66.4 mg, 0.3 mmol) and 2 mL of THF were added and the temperature was lowered to -78 ° C. The 1-naphthyllithium prepared above was slowly added and stirred under -78 ° C for 30 minutes. After 30 minutes, the mixture was brought to room temperature, and stirred for another 30 minutes to prepare tri (1-naphthyl) indium. The prepared tri (1-naphthyl) indium reagent was used directly for the cross-coupling reaction according to the following examples.

Preparation Example 2 Preparation of Tri (2-naphthyl) Indium Reagent

Tri (2-naphthyl) indium reagent was prepared using 2-bromonaphthalene (189.5 mg, 0.915 mmol) by the method described in Preparation Example 1, and was used directly in the cross-coupling reaction according to the following examples. .

EXAMPLE

Example 1. Preparation of 4,4'-bis (1-naphthyl) -1,1'-biphenyl.

In a reaction flask with reflux, 4,4'-diiodobiphenyl (121.8 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) was added and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 1.0 equivalent of tri (1-naphthyl) sodium, prepared in Preparation Example 1, was slowly added to the reaction flask and stirred at 70 ° C. for 7 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 4,4'-bis (1-naphthyl) -1,1'-biphenyl (95.1 mg, 78%) as a white solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.02 (d, J = 8.2 Hz, 2H), 7.93 (d, J = 7.7 Hz, 2H), 7.89 (d, J = 8.1 Hz, 2H), 7.82 (d , J = 8.1 Hz, 4H), 7.63 (d, J = 8.1 Hz, 4H), 7.58-7.46 (m, 8H).

Example 2. Preparation of 4,4'-bis (1-naphthyl) -1,1'-biphenyl.

4,4'-dibromobiphenyl (93.6 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 1.0 equivalent of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and stirred at 70 ° C for 10 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 4,4'-bis (1-naphthyl) -1,1'-biphenyl (90.6 mg, 74%) as a white solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.02 (d, J = 8.2 Hz, 2H), 7.93 (d, J = 7.7 Hz, 2H), 7.89 (d, J = 8.1 Hz, 2H), 7.82 (d , J = 8.1 Hz, 4H), 7.63 (d, J = 8.1 Hz, 4H), 7.58-7.46 (m, 8H).

Example 3. Preparation of 9,10-di (1-naphthyl) -anthracene.

9,10-dibromoanthracene (100.8 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 1.5 equivalent of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and stirred at 70 ° C. for 8 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent 10% CH ₂ Cl ₂ / hexane) to give a yellow solid 9,10-di (1-naphthyl) -anthracene (109.7 mg, 85%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.10 (d, J = 8.2 Hz, 2H), 8.04 (d, J = 8.2 Hz, 2H), 7.77-7.73 (m, 2H), 7.67 (d, J = 6.9 Hz, 2H), 7.53-7.48 (m, 6H), 7.28-7.20 (m, 8H).

Example 4. Preparation of 2,7-di (1-naphthyl) -9,9'-dimethylfluorene.

2,7-dibromofluorene (105.6 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 2.0 equivalents of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and stirred at 70 ° C. for 3 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 2,7-di (1-naphthyl) -9,9'-dimethylfluorene (98.1 mg, 73%) as a white solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.03 (d, J = 8.3 Hz, 2H), 7.94-7.87 (m, 6H), 7.60 (s, 2H), 7.58-7.44 (m, 10H), 1.59 ( s, 6H).

Example 5. Preparation of 3,6-di (1-naphthyl) -9-ethylcarbazole.

3,6-dibromo-9-ethylcarbazole (105.9 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto. Stirred at. Then, 2.0 equivalents of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and stirred at 70 ° C. for 4 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent 10% CH ₂ Cl ₂ / hexane) to give 3,6-di (1-naphthyl) -9-ethylcarbazole (98.1mg, 73%) as a white solid. Got.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.22 (s, 2H), 8.01 (d, J = 8.3 Hz, 2H), 7.91 (d, J = 8.0 Hz, 2H), 7.88-7.84 (m, 2H) , 7.64 (d, J = 8.3 Hz, 2H), 7.58-7.53 (m, 6H), 7.48 (d, J = 8.0 Hz, 2H), 7.41 (t, J = 8.3 Hz, 1H), 4.52 (q, J = 7.2 Hz, 2H), 1.58 (t, J = 7.2 Hz, 3H).

Example 6. Preparation of 5,5'-bis (1-naphthyl) -2,2'-bithiophene.

5,5'-Dibromo-2,2'-bithiophene (97.2 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and THF was After adding mL and stirred at room temperature. Then, 2.0 equivalents of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and stirred at 70 ° C. for 4 hours. The reaction was confirmed by TLC, and the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3) and washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl. The extracted organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 5,5`-5,5'-bis (1-naphthyl) -2,2'-bithiophene (74.5 mg, 59%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.34-8.32 (m, 2H), 7.91-7.85 (m, 4H), 7.61 (d, J = 7.0 Hz, 2H), 7.55-7.48 (m, 6H), 7.30 (d, J = 3.7 Hz, 2H), 7.18 (d, J = 3.70 Hz, 2H).

Example 7. Preparation of 2- (1-naphthyl) -9,9'-spirobifluorene.

2-bromo-9,9'-spirobifluorene (118.6 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto. Then stirred at room temperature. Then, 0.5 equivalent of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and heated to 70 ° C. After heating for 2 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent 5% CH ₂ Cl ₂ / hexane) to give 2- (1-naphthyl) -9,9'-spirobifluorene (119.2 mg, 90%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.95 (d, J = 7.8 Hz, 1H), 7.90 (d, J = 7.6 Hz, 1H), 7.82-7.78 (m, 3m), 7.74 (d, J = 8.3 Hz, 2H), 7.52 (d, J = 7.9 Hz, 1H), 7.42-7.27 (m, 7H), 7.15-7.11 (m, 3H), 6.84 (d, J = 7.3 Hz, 3H), 6.77 ( d, J = 7.6 Hz, 1H).

Example 8. Preparation of 1- (1-naphthyl) -pyrene

1-bromopyrene (84.4 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 0.75 equivalents of tri (1-naphthyl) indium prepared in Preparation Example 1 was slowly added to the reaction flask and heated to 70 ° C. After heating for 6 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 1- (1-naphthyl) -pyrene (74.5 mg, 76%) as a white solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.31 (d, J = 7.8 Hz, 1H), 8.24 (d, J = 7.6 Hz, 1H), 8.17 (dd, J = 8.8, 12.1 Hz, 3H), 8.06 -8.01 (m, 4H), 7.91 (d, J = 9.2 Hz, 1H), 7.70-7.63 (m, 3H), 7.52 (t, J = 7.4 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H), 7.32-7.28 (m, 1H).

Example 9. Preparation of 2- (4'-iodo [1,1'-biphenyl] -4-yl) -naphthalene.

4,4'-diiodobiphenyl (121.8 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 1.0 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 18 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 2- (4'-iodo [1,1'-biphenyl] -4-yl) -naphthalene (81.3 mg, 67 as a white solid). %) Was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.09 (s, 1H), 7.93 (t, J = 9.0 Hz, 2H), 7.88 (d, J = 6.8 Hz, 1H), 7.83-7.78 (m, 5H) , 7.70-7.67 (m, 2H), 7.55-7.48 (m, 2H), 7.41 (t, J = 8.8 Hz, 2H).

Example 10 Preparation of 2- (4'-bromo [1,1'-biphenyl] -4-yl) -naphthalene.

4,4'-dibromobiphenyl (93.61 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 1.0 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 18 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 2- (4'-bromo [1,1'-biphenyl] -4-yl) -naphthalene (80.5 mg, 68 as a white solid). %) Was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.09 (s, 1H), 7.93 (t, J = 9.0 Hz, 2H), 7.88 (d, J = 6.8 Hz, 1H), 7.83-7.78 (m, 5H) , 7.70-7.67 (m, 2H), 7.55-7.48 (m, 2H), 7.41 (t, J = 8.8 Hz, 2H).

Example 11. Preparation of 9,10-di- (2-naphthyl) -anthracene.

9,10-Dibromoanthracene (100.8 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 2.0 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 80 ° C. After heating for 12 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 9,10-di- (2-naphthyl) -anthracene (87.3 mg, 68%) as a yellow solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.1 (d, J = 8.3 Hz, 2H), 8.05-8.01 (m, 4H), 7.94 (d, J = 7.9 Hz, 2H), 7.75 (q, J = 3.4 Hz, 4H), 7.65-7.58 (m, 6H), 7.32 (q, J = 3.9 Hz, 4H).

Example 12. Preparation of 2,7-di (2-naphthyl) -9,9'-dimethylfluorene.

2,7-dibromo-9,9'-dimethylfluorene (105.6 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added. After the addition, the mixture was stirred at room temperature. Then, 2.0 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 3 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent 10% CH ₂ Cl ₂ / hexane) to give 2,7-di (2-naphthyl) -9,9'-dimethylfluorene (106.2 mg) as a white solid. , 79%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.13 (s, 2H), 7.97-7.81 (m, 12H), 7.74 (d, J = 7.8 Hz, 2H), 7.55-7.48 (m, 4H), 1.66 ( s, 6H).

Example 13. Preparation of 3,6-di (2-naphthyl) -9-ethylcarbazole.

3,6-dibromo-9-ethylcarbazole (105.9 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto. Stirred at. Then, 2.0 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 4 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent 10% CH ₂ Cl ₂ / hexane) to give 3,6-di (2-naphthyl) -9-ethylcarbazole (111.3 mg, 83% as a white solid). )

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.54 (s, 2H), 8.17 (s, 2H), 7.97-7.87 (m, 10H), 7.55-7.45 (m, 6H), 4.45 (q, J = 7.2 Hz, 2H), 1.51 (t, J = 7.2 Hz, 3H).

Example 14. Preparation of 2- (2-naphthyl) -9,9'-spirobifluorene.

2-dibromo-9,9'-spirobifluorene (118.6 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added. After the addition, the mixture was stirred at room temperature. Then, 0.5 equivalent of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 3 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated using column chromatography (developing solvent 5% CH ₂ Cl ₂ / hexane) to give 2- (2-naphthyl) -9,9'-spirobifluorene (108.7 mg, 82%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.87 (d, J = 7.9 Hz, 1H), 7.81-7.79 (m, 4H), 7.72-7.67 (m, 4H), 7.49 (d, J = 8.6 Hz, 1H), 7.35-7.29 (m, 5H), 7.07-7.00 (m, 4H), 6.73 (d, J = 7.6 Hz, 2H), 6.66 (d, J = 7.6 Hz, 1H).

Example 15 Preparation of 1- (2-naphthyl) -pyrene

1-bromopyrene (84.4 mg, 0.3 mmol) and Pd (dppf) Cl ₂ (17.6 mg, 0.024 mmol) were added to a reaction flask connected with a reflux apparatus, and 2 mL of THF was added thereto, followed by stirring at room temperature. Then, 0.75 equivalents of tri (2-naphthyl) indium prepared in Preparation Example 2 was slowly added to the reaction flask and heated to 70 ° C. After heating for 2 hours the reaction was terminated with MeOH (2 mL). The aqueous layer was extracted with EtOAc (20 mL × 3), washed with 20 mL of 5% HCl, 20 mL of saturated NaHCO _{3 and} 20 mL of saturated NaCl, and the organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed and separated by column chromatography (developing solvent: hexane) to give 1- (2-naphthyl) -pyrene (88.0 mg, 89%) as a white solid.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (t, J = 8.5 Hz, 2H), 8.23 (d, J = 7.5 Hz, 1H), 8.19 (d, J = 7.3 Hz, 1H), 8.13-8.09 (m, 4H), 8.06-7.96 (m, 5H), 7.81 (d, J = 8.4 Hz, 1H), 7.60 (q, J = 6.3 Hz, 1H). 7.59 (d, J = 6.2 Hz, 1H).

In the preparation method according to the present invention, the naphthyl halide obtained from the reaction between naphthyl halide and BuLi is treated with indium chloride (InCl ₃ ), and the naphthyl indium reagent is variously prepared in-situ without any additional purification process. By cross-coupling the electrophilic aromatic compound, an aromatic polycyclic compound having a naphthyl group represented by Chemical Formula 1 may be synthesized with excellent yield.

In addition, aromatic polycyclic compounds having a naphthyl group represented by Formula 1 according to the present invention are useful as an organic electroluminescent material and a liquid crystal material.

Claims (9)

An aromatic polycyclic compound having a naphthyl group represented by Formula 1 below: [Formula 1]

In Chemical Formula 1,

Is 1,1'-biphenyl, 4-iodo-1,1'-biphenyl, 4-bromo-1,1'-biphenyl, 9,10-anthracenyl, fluorenyl, 9,9 ' -Dimethyl fluorenyl, carbazolyl, 9-ethylcarbazolyl, 2,2'-bithiophenyl, 9,9'-spirobifluorenyl, and 1-pyrenyl, The aromatic multiring is halogen, C ₁ -C ₆ alkylsulfonate, phenylsulfonate, 4-trifluoromethylphenylsulfonate, trifluoromethanesulfonate, and diazonium salt [N ₂ Y wherein Y is Cl , Br, I)] may be substituted or unsubstituted with a substituent selected from; n is an integer of 1 or 2. The method of claim 1, 4,4'-bis (1-naphthyl) -1,1'-biphenyl, 9,10-di (1-naphthyl) -anthracene, 2,7-di (1-naphthyl) -9,9'-dimethylfluorene, 3,6-di (1-naphthyl) -9-ethylcarbazole, 5,5'-bis (1-naphthyl) -2,2'-bithiophene, 2- (1-naphthyl) -9,9'-spirobifluorene, 1- (1-naphthyl) -pyrene, 2- (4'-iodo [1,1'-biphenyl] -4-yl) -naphthalene 2- (4'-Bromo [1,1'-biphenyl] -4-yl) -naphthalene 9,10-di- (2-naphthyl) -anthracene, 2,7-di (2-naphthyl) -9,9'-dimethylfluorene, 3,6-di (2-naphthyl) -9-ethylcarbazole, 2- (2-naphthyl) -9,9'-spirobifluorene, Compound selected from 1- (2-naphthyl) -pyrene. Method for producing an aromatic polycyclic compound having a naphthyl group comprising the following manufacturing process: After the naphthyl halide represented by the following Chemical Formula 2 and butyllithium were reacted to prepare naphthyl lithium, and then reacted with indium chloride (InCl ₃ ) to prepare a naphthyl indium reagent represented by the following Chemical Formula 3,

In the above scheme, X is a halogen atom; A crosslinking reaction of a naphthyl indium reagent represented by the following Chemical Formula 3 with an aromatic polycyclic compound represented by the following Chemical Formula 4 in the presence of a transition metal catalyst to prepare an aromatic polycyclic compound having a naphthyl group represented by the following Chemical Formula 1 process;

In the above scheme, X is hydrogen atom, halogen atom, C ₁ -C ₆ alkylsulfonate, phenylsulfonate, 4-trifluoromethylphenylsulfonate, trifluoromethanesulfonate, and diazonium salt [N ₂ Y ( In this case, Y is Cl, Br, I)] n substituents selected from, except when the substituents (X) are all hydrogen atoms, n is an integer of 1 or 2. The method of claim 3, wherein the preparation is performed in situ without separation and purification of the naphthyl indium reagent represented by Chemical Formula 3. The method of claim 3, wherein And the catalyst used in the cross-coupling reaction is a palladium (Pd) metal-containing compound. The method of claim 5, wherein The catalysts used in the cross-coupling reaction are (dppf) PdCl ₂ , Pd (PPh ₃ ) ₄ , (PPh ₃ ) ₂ PdCl ₂ , (DPEphos) PdCl _{2 ,} PdCl ₂ , Pd (OAc) ₂ , and Pd ( CH ₃ CN) ₂ Cl ₂ A palladium (Pd) metal-containing compound selected from the manufacturing method characterized in that. The method of claim 3, wherein The aromatic polycyclic compound represented by Formula 4 is a production method characterized in that the electrophile selected from the group consisting of the following compounds:

In the compound, R ₁ and R ₂ each represent a hydrogen atom or a C ₁ -C ₆ alkyl group; X ₁ and X ₂ are each a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkylsulfonate group, a phenylsulfonate group, 4-trifluoromethylphenylsulfonate, trifluoromethanesulfonate, and a diazonium salt [N ₂ Y (where Y is Cl, Br, I)], except when both X ₁ and X ₂ are hydrogen atoms at the same time. The method of claim 3, wherein The naphthyl indium reagent represented by Chemical Formula 3 is used in an amount ranging from 0.5 to 2 equivalents based on the aromatic polycyclic compound represented by Chemical Formula 4. The method of claim 3, wherein The cross-coupling reaction is carried out under the conditions of reflux under a solvent of tetrahydrofuran (THF).