KR102020842B1 - Intermediate for making phenanthroline, method of making the same and method of making phenanthroline using the same - Google Patents

Abstract

The present invention relates to novel compound for easily manufacturing a phenanthroline compound substituted with substituents at positions 2 and/or 9 of phenanthroline. In addition, the present invention relates to the novel compound and a method for manufacturing the phenanthroline compound manufactured from the same. According to the present invention, it is possible to reduce a reaction step to facilitate mass production.

Description

Compound for the preparation of phenanthroline, preparation method thereof and preparation method of the phenanthroline compound using the same {INTERMEDIATE FOR MAKING PHENANTHROLINE, METHOD OF MAKING THE SAME AND MATH PHENANTHROLINE USING THE SAME}

The present invention relates to a compound for easily preparing a phenanthroline compound substituted at positions 2 and / or 9 with a substituent, and a method for preparing the same. The present invention also relates to a process for preparing the phenanthroline compound prepared therefrom.

Organic Light Emitting Device, one of the next generation display technologies replacing the liquid crystal display, is actively developed in various industrial fields and is becoming the next device manufacturing and display technology. The organic light emitting device has to form an optimal energy bend gap in order to efficiently transfer electrons and holes from the power source by stacking a plurality of thin film organic material layers, and thermal chemical stability is required due to the characteristics of the vacuum deposition process. Among the materials of the organic light emitting device, phenanthroline, which is widely used as an electron injection layer, an electron transport layer, a charge generation layer, a light emitting material, and a host material, is a compound that can be easily synthesized. However, in order to improve the thermal stability of phenanthroline, various synthetic methods for introducing various substituents simultaneously at positions 2 and 9 of phenanthroline, for example, a low temperature reaction (below 0 ° C.), or a multistage reaction Although a method such as Suzhou key reaction has been tried, there is a disadvantage that mass production is not easy.

Patent Document 1: Korean Patent Publication No. 10-2015-0054797

It is an object of the present invention to provide a compound for preparing phenanthroline and a method for preparing the same, which can improve the unit cost of a product by reducing the reaction step to secure high yield and ease of mass production. It is also an object of the present invention to provide a process for the preparation of phenanthroline compounds using such compounds.

The object of the present invention can be achieved by a compound represented by the following formula (1) used for the preparation of phenanthroline:

[Formula 1]

(In Formula 1, R is deuterium; halogen group; substituted or unsubstituted C1 to C60 linear or branched alkyl group; substituted or unsubstituted C2 to C60 straight or branched alkenyl group; substituted or unsubstituted. C2 to C60 linear or branched alkynyl group; substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; and substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group.

R may be selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline.

In addition, an object of the present invention is a method for preparing a compound represented by the following formula (1), the step of forming a first intermediate product by substituting R of Cl atoms of the starting material represented by the formula (2), the first intermediate Replacing the methyl group with a carbonyl group to form a second intermediate product, and replacing the O atom of the NO ₂ group of the second intermediate product with a hydrogen atom to form a compound represented by the following Formula 1, wherein R Silver deuterium; Halogen group; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; And substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl groups.

[Formula 1]

[Formula 2]

.

.

Formation of the first intermediate may include reacting the starting material with R-boronic acid.

R may be selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline.

The second intermediate may be formed by reaction with sodium periodate after the reaction between the first intermediate and N, N-dimethylformamide dimethyl acetal (DMFDMA: N, N-dimethylformamide dimethyl acetal). .

The compound represented by Chemical Formula 1 may be formed by reaction of the second intermediate product with calcium chloride and iron powder.

In addition, an object of the present invention is to be achieved by a method for producing a phenanthroline compound represented by the following formula (4) comprising the step of reacting a compound represented by the formula (1) and a compound represented by the formula (3) Can:

[Formula 1]

[Formula 3]

[Formula 4]

Wherein R is deuterium; a halogen group; a substituted or unsubstituted C1 to C60 linear or branched alkyl group; a substituted or unsubstituted C2 to C60 straight or branched alkenyl group; substituted or unsubstituted C2 to C60 linear or branched alkynyl group; substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group, and substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group, A is hydrogen, substituted or unsubstituted aryl group having 6 to 60 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms and an alkyl group having 1 to 20 carbon atoms.)

R may be selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline.

According to the present invention there is provided a novel compound for producing a phenanthroline compound widely used as an organic light emitting device material and a method for producing the same. Also provided are methods of preparing phenanthroline compounds using such compounds.

According to the present invention, it is possible to reduce the reaction step without a low temperature reaction step to facilitate mass production, compared to the existing multi-step reaction method of introducing aryl or heteroaryl at positions 2 and 9 in order to increase the stability of phenanthroline. At the same time, the unit price can be improved.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

Compounds of the present invention used to prepare phenanthroline compounds are represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R is deuterium; Halogen group; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; And a substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group.

Wherein R is specifically, R may be selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline, but is not limited thereto.

The compound of the present invention provides a starting material, 2-chloro-7-methyl-8-nitroquinoline (CAS No .: 90767-44-5), by substituting R for Cl atoms of the starting material to a first intermediate Forming a product, replacing the methyl group of the first intermediate product with a carbonyl group to form a second intermediate product, and replacing the O atom of the NO ₂ group of the second intermediate product with a hydrogen atom, It can be prepared by a method comprising the step of forming a compound. Wherein R is deuterium; Halogen group; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; And it may be selected from the group consisting of substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group.

R is specifically as mentioned above.

More specifically, 8-amino-2-R-quinoline-7-carbaldehyde, which is a compound of the present invention, may be prepared as in Scheme 1 below.

Scheme 1

Referring to Scheme 1, the starting material 2-chloro-7-methyl-8-nitroquinoline is subjected to Suzuki reaction with R-boronic acid to form a first intermediate product. The first intermediate product reacts with N, N-dimethylformamide dimethyl acetal (DMFDMA) and then with sodium periodate to form a second intermediate product. The product reacts with calcium chloride and iron powder to form 8-amino-2-R-quinoline-7-carbaldehyde, a compound of the present invention.

R is specifically as mentioned above.

More specifically, 8-amino-2-phenyl-quinoline-7-carbaldehyde, which is an example of the present invention, may be prepared according to Scheme 2 below.

Scheme 2

Referring to Scheme 2, the starting material 2-chloro-7-methyl-8-nitroquinoline reacts with phenylboronic acid for several weeks to form a first intermediate product. This first intermediate product is reacted with N, N-dimethylformamide dimethyl acetal and then with sodium periodate to form a second intermediate product. The second intermediate product is reacted with calcium chloride and iron powder. One example of the compound is 8-amino-2-phenyl-quinoline-7-carbaldehyde.

Using the compound of the present invention prepared in this way it is possible to easily prepare a phenanthroline R is substituted in position 2 and / or position 9.

More specifically, only the step of reacting the compound represented by the following Chemical Formula 1 and the compound represented by the following Chemical Formula 3 may be easily prepared.

[Formula 1]

[Formula 3]

[Formula 4]

In the above formula,

R is deuterium; Halogen group; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group,

A is selected from the group consisting of hydrogen, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, and an alkyl group having 1 to 20 carbon atoms.

R is specifically as mentioned above.

As described above, by applying the compound of the present invention, 8-amino-2-R-quinoline-7-carbaldehyde, to the preparation of the phenanthroline compound, phenanthroline 2 may be used to improve molecular stability after phenanthroline synthesis. And compared to the conventional high difficulty low temperature reaction process or multi-stage process technology that substitutes a substituent such as phenyl at position 9, it is possible to reduce the number of processes without the low temperature reaction step to secure high yield and mass production, and at the same time improve the cost Can be.

Specifically, by applying 8-amino-2-R-quinoline-7-carbaldehyde as a compound of the present invention as an intermediate, the following compounds can be prepared.

Hereinafter, examples of the compound according to the present invention will be described. However, the examples described below are merely for illustrating or explaining the present invention in detail, and the present invention should not be limited to and interpreted by the examples described below.

Example

(Production Example of Intermediate T-5)

Synthesis of T-2

10 g of 2-chloro-7-methyl-8-nitroquinoline (CAS No .: 90767-44-5), 7.1 g of phenylboronic acid, 2 g of Pd (PPh ₃ ) ₄ and 24.8 g of K ₂ CO ₃ were rounded The flask was refluxed with toluene, EtOH, and water for 2-3 hours. After completion of the reaction by thin layer chromatography (TLC: Thin Film Chromatography) was extracted with MC and water and the organic layer was distilled. Thereafter, the mixture was recrystallized from MeOH, acetone and water, and dried to obtain 10 g of T-2.

¹ H-NMR (CDCl ₃ , ppm): 8.23-8.182 (m, 3H), 7.98 (d, 1H), 7.83 (d, 1H), 7.52-7.45 (m, 3H), 7.39 (d, 1H), 2.55 (s, 3 H).

MS: [M + H] ⁺ = 265.1

Synthesis of T-3

10 g of T-2 and 13.4 g of dimethyl acetal (DMFDMA) were stirred in 120 ml of dimethylformamide (DMF) at 140 ° C. for 16 hours, and the reaction was extracted with MC and water. The organic layer was distilled off and recrystallized from MeOH, acetone and water to obtain 8.9 g of T-3.

¹ H-NMR (CDCl ₃ , ppm): 8.17 (d, 2H), 8.06 (d, 1H), 7.79 (d, 1H), 7.64 (d, 1H), 7.53-7.43 (m, 5H), 7.10 ( d, 1H), 5.12 (d, 1H), 2.94 (s, 6H).

MS: [M + H] ⁺ = 320.1

Synthesis of T-4

8.9 g of T-3 and 23.4 g of AC were stirred in 530 ml of THF (Tetrahydrofuran) for 15 hours. The pH of the reaction solution was neutralized to 7-9 with NaOH aqueous solution. After filtration and washing with MC, the filtrate was crystallized by distillation. The crystals were slurried with EtOH and filtered to give 6.8 g of T-4.

¹ H-NMR (CDCl ₃ , ppm): 10.24 (s, 1H), 8.34 (d, 1H), 8.21-8.2 (m, 2H), 8.16 (d, 1H), 8.08 (d, 1H), 8.02 ( d, 1H), 7.55-7, 51 (m, 3H).

MS: [M + H] ⁺ = 279.0

Synthesis of T-5

6.8 g of T-4, 4.1 g of CaCl _{2 and} 6.5 g of iron powder were dissolved in 120 ml of EtOH and refluxed for 15 hours. The reaction was filtered and washed with MC and the filtrate was extracted with brine and MC. The organic layer was distilled and recrystallized by IPE to obtain 3.5 g of T-5.

¹ H-NMR (CDCl ₃ , ppm): 10.0 (s, 1H), 8.16-8.14 (m, 2H), 8.09 (d, 1H), 7.98 (d, 1H), 7.55-7.46 (m, 5H), 7.01 (d, 1 H).

MS: [M + H] ⁺ = 249.1

(Production Example of Compound)

Preparation Example 1

Synthesis of Compound 1

15 g of 1- (4- (phenanthren-9-yl) naphthalen-1-yl) ethanone, 11.8 g of T-5, and 4.8 g of KOH were dissolved in 120 mL of toluene and 75 mL of EtOH and refluxed for 6 hours. The reaction solution was extracted with MC and water, and the organic layer was distilled off and recrystallized with IPr to obtain 20 g as compound 1.

Preparation Example of Compound 2

Synthesis of 1- (4 '-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl] -4-yl) ethanone

15 g of 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine, 7.6 g of (4-acetylphenyl) boronic acid, 1.3 g of Pd (PPh ₃ ) ₄ , 18.6 g of K ₂ CO ₃ It was refluxed for 6 hours in toluene, ethanol and water. The reaction solution was recrystallized with excess ethanol and water to obtain 1- (4 '-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl] -4-yl) ethanone 16 g was obtained.

Synthesis of Compound 2

15 g 1- (4 '-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl] -4-yl) ethanone, 9.6 g T-5, KOH 4.3 g was dissolved in 150 mL of toluene and 75 mL of ethanol and refluxed for 5 hours. The reaction solution was extracted with MC and water, and the organic layer was distilled and recrystallized with IPr to obtain 12 g as compound 2.

Preparation Example of Compound 3

Synthesis of 1- (4 '-([3,2': 6 ', 3' '-terpyridin] -4'-yl)-[1,1'-biphenyl] -4-yl) ethanone

4 '-(4-bromophenyl) -3,2': 6 ', 3''-terpyridine 11 g, (4-acetylphenyl) boronic acid 11.9 g, Pd (PPh ₃ ) ₄ 0.8 g, K ₂ CO ₃ 12 g Was dissolved in 110 mL of toluene, 50 mL of ethanol, 50 mL of water and refluxed for 6 hours. The reaction solution was recrystallized with excess methanol and water to give 1- (4 '-([3,2': 6 ', 3''-terpyridin]-4'-yl)-[1,1'-biphenyl] -4- 16 g of yl) ethanone were obtained.

Synthesis of Compound 3

1- (4 '-([3,2': 6 ', 3' '-terpyridin] -4'-yl)-[1,1'-biphenyl] -4-yl) ethanone 15 g, T-5 9 g and 4.8 g of KOH were dissolved in 150 mL of toluene and 75 mL of ethanol and refluxed for 7 hours. The reaction solution was extracted with MC and water, and the organic layer was distilled and recrystallized with IPr to obtain 10 g as compound 3.

Preparation Example of Compound 4

Synthesis of 1- (4- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) naphthalen-1-yl) ethanone

2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine 15 g, 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 13.7 g of yl) naphthalen-1-yl) ethanone, 1.3 g of Pd (PPh ₃ ) ₄ , and 18.6 g of K ₂ CO ₃ were dissolved in 150 mL of toluene, 75 mL of ethanol, 75 mL of water, and refluxed for 5 hours. The reaction solution was extracted with MC and water, and the organic layer was distilled and recrystallized with IPr to obtain 1- (4- (4- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) naphthalen-1-yl 16 g of ethanone was obtained.

Synthesis of Compound 4

16 g of 1- (4- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) naphthalen-1-yl) ethanone, 9.1 g T-5, 4.1 g KOH toluene It was dissolved in 160 mL, 80 mL of ethanol and refluxed for 5 hours. The reaction solution was recrystallized from excess ethanol and water to give 17.3 g as compound 4.

Preparation Example of Compound 5

Synthesis of 1- (4- (9,10-diphenylanthracen-2-yl) phenyl) ethanone

3.6 g of 1- (4-bromophenyl) ethanone, 10 g of 2- (9,10-diphenylanthracen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 10 g, Pd (PPh ₃ ) ₄ 630 mg, K ₂ CO _3, 8.8 g, was dissolved in 40 mL of toluene, 20 mL of ethanol, 20 mL of water and refluxed for 5 hours. The reaction solution was extracted with MC and water, and the organic layer was distilled and recrystallized with IPr to obtain 7.6 g of 1- (4- (9,10-diphenylanthracen-2-yl) phenyl) ethanone.

Synthesis of Compound 5

6.7 g of 1- (4- (9,10-diphenylanthracen-2-yl) phenyl) ethanone, 4.6 g of T-5, and 1.9 g of KOH were dissolved in 60 mL of toluene and 40 mL of ethanol and refluxed for 5 hours. The reaction solution was recrystallized from excess ethanol and water to obtain 8.4 g as compound 5.

NMR data of the compounds 1 to 5 are as follows.

Fabrication of Organic EL Device

1. Preparation Example 1

After patterning the ITO board | substrate so that a light emitting area might be 2 mm x 2 mm, it wash | cleaned respectively with isopropyl alcohol and UV ozone. Thereafter, the ITO substrate was mounted on the substrate holder of the vacuum deposition apparatus and pressure was applied such that the vacuum degree was 1 × 10 ⁻⁷ torr. Thereafter, plasma treatment was performed for 3 minutes under N ₂ atmosphere.

First, a HAT-CN compound was vacuum deposited to form a 5 nm thick. This compound acts as a hole injection layer. An NPB material was formed to a thickness of 50 nm as a first hole transport layer thereon. Subsequently, the HT-1 material was formed to a thickness of 10 nm as the second hole transport layer.

Thereafter, the GH-1 material was co-deposited at a thickness of 30 nm such that the GD-1 material was doped with a dopant to about 10% by mass to form a green light emitting layer.

On this light emitting layer, an ET-1 compound was formed to an electron transport layer having a thickness of 35 nm. Then, LiF material was deposited to form an electron injection layer having a thickness of 1 nm. Thereafter, Al was deposited to a thickness of 100 nm to form a cathode to fabricate an organic EL device.

2. Preparation Example of Comparative Example 2

The organic light emitting device was fabricated in the same manner as the comparative example described above, except that only the electron transport layer material ET-1 was changed to ET-2.

3. Preparation Example 1

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transporting material ET-1 with Compound 1.

4. Preparation Example 2

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transporting material ET-1 with Compound 2.

5. Preparation Example 3

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transport layer material ET-1 with compound 3.

6. Preparation Example 4

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transporting material ET-1 with Compound 4.

The luminescence properties were measured by PR-670 of Photoresearch by applying a constant current of 10 mA / cm ² to the organic light emitting diodes prepared according to Examples 1 to 4 and Comparative Examples 1 to 2 of the present invention. It was.

Hereinafter, the current density, driving voltage, current efficiency, and external quantum efficiency of the organic light emitting diodes of Examples 1 to 4 and Comparative Examples 1 and 2 were measured and shown in Table 1 below.

matter Drive current
J (mA / cm ² ) Driving voltage
(Voltage) Current efficiency
(cd / A) EQE
(%) Comparative Example 1 ET-1 10 3.5 44.7 14.2 Comparative Example 2 ET-2 10 3.88 55.2 17.9 Example 1 Compound 1 10 3.46 61.7 19.7 Example 2 Compound 2 10 3.44 60.4 19.3 Example 3 Compound 3 10 3.64 60.3 19.2 Example 4 Compound 4 10 3.43 58.1 18.6

It can be seen that the current efficiency and EQE of Examples 1 to 4 are improved compared to Comparative Examples 1 and 2.

The present invention is not necessarily limited to these embodiments, and various modifications can be made without departing from the spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (10)

Compounds represented by the following formula (1) used to prepare phenanthroline having substituents at positions 2 and 9:
[Formula 1]

In Chemical Formula 1,
R is deuterium; Halogen group; C1 to C60 straight or branched chain alkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkenyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkynyl group unsubstituted or substituted with aryl or heteroaryl; C3 to C60 monocyclic or polycyclic cycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 monocyclic or polycyclic heterocycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C6 to C60 monocyclic or polycyclic aryl group unsubstituted or substituted with aryl or heteroaryl; And C2 to C60 monocyclic or polycyclic heteroaryl groups unsubstituted or substituted with aryl or heteroaryl. The compound of claim 1, wherein R is selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl, and isoquinoline. As a method for producing a compound represented by the following formula (1) used for the preparation of phenanthroline having a substituent at positions 2 and 9,
Replacing the Cl atom of the starting material represented by Formula 2 with R to form a first intermediate product,
Replacing the methyl group of the first intermediate product with a carbonyl group to form a second intermediate product, and
Replacing the O atom of the NO ₂ group of the second intermediate product with a hydrogen atom to form a compound represented by Formula 1 below
Including,
R is deuterium; Halogen group; C1 to C60 straight or branched chain alkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkenyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkynyl group unsubstituted or substituted with aryl or heteroaryl; C3 to C60 monocyclic or polycyclic cycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 monocyclic or polycyclic heterocycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C6 to C60 monocyclic or polycyclic aryl group unsubstituted or substituted with aryl or heteroaryl; And a C2 to C60 monocyclic or polycyclic heteroaryl group substituted or unsubstituted with aryl or heteroaryl.
[Formula 1]

[Formula 2]

. The method of claim 3,
Formation of the first intermediate product,
And reacting the starting material with R-boronic acid. 5. The process according to claim 3, wherein R is selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline. The method of claim 3, wherein the second intermediate is reacted with sodium periodate after reaction of the first intermediate with N, N-dimethylformamide dimethyl acetal (DMFDMA). It is formed by. The method of claim 3, wherein the compound represented by Chemical Formula 1 is formed by reaction of the second intermediate with calcium chloride and iron powder. As a method for producing a phenanthroline compound represented by the formula (4),
A manufacturing method comprising the step of reacting a compound represented by the formula (1) and a compound represented by the formula (3):
[Formula 1]

[Formula 3]

[Formula 4]

In the above formula,
R is deuterium; Halogen group; C1 to C60 straight or branched chain alkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkenyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 straight or branched chain alkynyl group unsubstituted or substituted with aryl or heteroaryl; C3 to C60 monocyclic or polycyclic cycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C2 to C60 monocyclic or polycyclic heterocycloalkyl group unsubstituted or substituted with aryl or heteroaryl; C6 to C60 monocyclic or polycyclic aryl group unsubstituted or substituted with aryl or heteroaryl; And it is selected from the group consisting of C2 to C60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted with aryl or heteroaryl,
A is a C6-C60 aryl group unsubstituted or substituted with hydrogen, aryl or heteroaryl, a C3-C60 heteroaryl group unsubstituted or substituted with aryl or heteroaryl, and a C1-C20 alkyl group Is selected from. The method of claim 8, wherein R is selected from the group consisting of phenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline, biphenyl and isoquinoline. The method of claim 8, wherein the phenanthroline compound is selected from the group consisting of the compounds represented by: