KR102095584B1 - A method for manufacturing deuterated organic compounds for OLED light emitting material - Google Patents

Abstract

The present invention relates to a method for producing a deuterated organic compound for an OLED light emitting material, and more specifically 9H-carbazole and 2-phenylpyridine are directly deuterium substituted using a microwave reactor to shorten the reaction time and deuterium substitution rate. It relates to a method for producing a deuterated organic compound for an OLED light emitting material that can improve the.

Description

A method for manufacturing deuterated organic compounds for OLED light emitting material}

The present invention relates to a method for producing a deuterated organic compound for an OLED light emitting material, and more specifically 9H-carbazole and 2-phenylpyridine are directly deuterium substituted using a microwave reactor to shorten the reaction time and deuterium substitution rate. It relates to a method for producing a deuterated organic compound for an OLED light emitting material that can improve the.

The flat panel display device plays a very important role in supporting a highly image-information society centering on the Internet, which has been showing rapid growth in recent years. In particular, the organic light emitting diode (OLED) capable of driving a low voltage in a self-emission type has superior viewing angle and contrast ratio compared to a liquid crystal display (LCD), which is the mainstream of a flat panel display device, and requires no backlight, so that it is light and thin. It is possible, and also has an advantage in terms of power consumption. Also, it has attracted attention as a next-generation display device due to its fast response speed and wide color reproduction range.

In general, an organic light emitting diode is formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode (cathode). In this case, the organic thin film is a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (electron injection layer) in addition to the light emitting layer (emitting layer, EML). layer, EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to the light emission characteristics of the light emitting layer.

When an electric field is applied to the organic light emitting diode having such a structure, holes are injected from the anode and electrons are injected from the cathode, and the injected holes and electrons are recombined in the light emitting layer through the hole transport layer and the electron transport layer, respectively, to emit light. To form. The formed luminescence excitation emits light while transitioning to the ground states. In this case, the luminescent dye (guest) is doped to the luminescent layer (host) to increase the efficiency and stability of the luminescent state.

In recent years, it has been known that not only fluorescent light-emitting materials but also phosphorescent light-emitting materials can be used as light-emitting materials of organic light-emitting diodes, and these phosphorescence light-emitting electrons transition from the ground state to the excited state, and then through intersystem crossing. It consists of a mechanism in which a singlet exciton is non-light-transmitted to a triplet exciton, and then a triplet exciton transitions to the ground state and emits light. At this time, since the triplet exciton is transferred, it cannot be directly transferred to the ground state (spin forbidden), so it undergoes the process of transitioning to the ground state after the flipping of the electron spin, so the life span (luminescence time) rather than fluorescence (lifetime) It has a longer property. That is, the emission duration of the fluorescent light emission is only a few nanoseconds, but in the case of the phosphorescence emission, it corresponds to a relatively long time, several microseconds.

The main issues of organic light emitting diodes using phosphorescent materials are life and stability, and various derivatives have been developed and used as phosphorescent materials to improve these properties.

Prior studies confirmed that the stability of the device was improved and the life was extended at high current density by deuterium substitution of the iridium organometallic compound (J. Mater. Chem. C., 2013, 1, 4821-4825).

However, the above method does not produce a deuterium-substituted compound by directly deuterium-substituting the starting material, but synthesizes an intermediate by deuterium-substituting the starting material, and then synthesizes the intermediate to synthesize a deuterium-substituted compound. It has a disadvantage that the time is very long, 48 hours, and the deuterium substitution rate is low.

Therefore, there is a need for a new production method capable of shortening the reaction time and improving the deuterium substitution rate by directly deuterating the starting material.

Korean Registered Patent No. 10-0685398 (2007.02.22)

The present invention has been devised in accordance with the above-mentioned requirements, for an OLED light-emitting material capable of shortening the reaction time and improving deuterium substitution rate by directly deuterium substitution of 9H-carbazole and 2-phenylpyridine using a microwave reactor. It is an object to provide a method for producing a deuterated organic compound.

The present invention relates to a deuterated compound for an OLED having a structure of Formula 1 or a structure of Formula 2 below.

[Formula 1]

[Formula 2]

In addition, the present invention

a) preparing a first reactant by mixing D ₂ O, the compound of Formula 3, and a catalyst;

b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And

c) extracting the second reactant to obtain a compound of Formula 1 below;

It relates to a method for producing a deuterated compound for OLED comprising a.

[Formula 3]

[Formula 1]

In addition, the present invention

a) preparing a first reactant by mixing D ₂ O, a compound of Formula 4, and a catalyst;

b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And

c) extracting the second reactant to obtain a compound of Formula 2 below;

It relates to a method for producing a deuterated compound for OLED comprising a.

[Formula 4]

[Formula 2]

In one embodiment of the present invention, the step a) is characterized in that 0.5 to 10 parts by weight of the compound of Formula 3 and 0.1 to 1 part by weight of the catalyst are used relative to 100 parts by weight of D ₂ O.

In one embodiment of the present invention, step a) is characterized in that 0.5 to 10 parts by weight of a compound of Formula 4 and 0.1 to 1 part by weight of a catalyst are used relative to 100 parts by weight of D ₂ O.

In one embodiment of the present invention, step b) is characterized in that is performed at 100 ~ 160 ℃.

In addition, the present invention relates to an organic light emitting diode comprising the deuterated compound for OLED in a light emitting layer.

The present invention provides a method for producing a deuterated organic compound for an OLED light emitting material that can shorten the reaction time and improve the deuterium substitution rate by directly deuterium-substituting 9H-carbazole and 2-phenylpyridine using a microwave reactor. You can.

The deuterated compound of the present invention can be applied to the light emitting layer of an organic light emitting diode to improve the life, stability and efficiency of a device.

1 shows the ¹ H NMR spectrum of deuterated 9H-carbazole.
2 shows the ¹ H NMR spectrum of deuterated 2-phenylpyridine.

The present invention can be modified in various ways and can have various embodiments, and thus, specific embodiments will be illustrated and described in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and it should be understood that all modifications, equivalents, and substitutes included in the spirit and scope of the present invention are included. In describing the present invention, detailed descriptions of related well-known technologies are omitted when it is determined that the subject matter of the present invention may be obscured.

Terms including ordinal numbers such as first and second may be used to describe various components, but the corresponding components are not limited by these terms. These terms are only used to distinguish one component from another.

When an element is said to be 'connected' to another component, or when it is said to be 'connected', it may be directly connected to or connected to the other component, but other components may exist in the middle. It should be understood that. On the other hand, when a component is said to be 'directly connected' or 'directly connected' to another component, it should be understood that no other component exists in the middle.

The terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as 'comprises' or 'have' are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

The present invention relates to a deuterated compound for an OLED having a structure of Formula 1 or a structure of Formula 2 below.

[Formula 1]

[Formula 2]

The deuterated compound may be applied to the light emitting layer of the organic light emitting diode to improve the life, stability, and efficiency of the device.

The deuterated compound can be prepared by directly replacing deuterium with 9H-carbazole (compound of formula 3) and 2-phenylpyridine (compound of formula 4) using a microwave reactor.

At this time, by appropriately adjusting the reaction conditions of the microwave reactor, it is possible to shorten the reaction time and improve the deuterium substitution rate.

In addition, the present invention comprises the steps of: a) preparing a first reactant by mixing D ₂ O, a compound of Formula 3 below, and a catalyst;

b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And

c) extracting the second reactant to obtain a compound of Formula 1 below;

It relates to a method for producing a deuterated compound for OLED comprising a.

[Formula 3]

[Formula 1]

Wherein the a) comprises: D ₂ O 100 parts by weight of that formula (3) compound of 0.5 to 10 parts by weight of the catalyst 0.1 to 1 parts by weight of is used, and preferably against, D ₂ O, wherein the value content of the compound and the catalyst of formula (3) When the range is satisfied, the reaction time can be shortened and the deuterium substitution rate can be increased.

As the catalyst, Pt / C, Pd / C, and the like can be used without limitation, and Pt / C is preferably used.

The compound of Formula 3 and the catalyst are preferably used in a weight ratio of 3 to 10: 1, and when the weight ratio satisfies the numerical range, the reaction time may be shortened and the deuterium substitution rate may be increased.

The step b) is preferably performed for 30 minutes to 2 hours at 100 to 160 ° C, and when the reaction temperature and reaction time satisfy the above numerical range, deuterium substitution rate may be increased.

At this time, the power of the microwave reactor is preferably 50 ~ 200W, and if the numerical range is satisfied, the reaction time can be shortened and the deuterium substitution rate can be increased.

In addition, the deuterium substitution rate of the compound may be improved by repeating the step b) two or more times.

In step c), the methylene chloride layer is separated by extracting the second reactant with methylene chloride and water, and the separated methylene chloride layer is dried to obtain a compound of Formula 1.

In addition, the present invention comprises the steps of preparing a first reactant by mixing a) D ₂ O, a compound of Formula 4 and a catalyst;

b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And

c) extracting the second reactant to obtain a compound of Formula 2 below;

It relates to a method for producing a deuterated compound for OLED comprising a.

[Formula 4]

[Formula 2]

Wherein the a) comprises: D ₂ O with respect to 100 parts by weight, preferably compounds of 0.5 to 10 parts by weight of the catalyst 0.1 to 1 parts by weight of the formula (4) is used, D ₂ O, wherein the value content of the compound and the catalyst of formula (IV) When the range is satisfied, the reaction time can be shortened and the deuterium substitution rate can be increased.

As the catalyst, Pt / C, Pd / C, and the like can be used without limitation, and Pd / C is preferably used.

The compound of Formula 4 and the catalyst are preferably used in a weight ratio of 3 to 10: 1, and when the weight ratio satisfies the numerical range, the reaction time may be shortened and the deuterium substitution rate may be increased.

The step b) is preferably performed for 30 minutes to 2 hours at 100 to 160 ° C, and when the reaction temperature and reaction time satisfy the above numerical range, deuterium substitution rate may be increased.

At this time, the power of the microwave reactor is preferably 50 ~ 200W, and if the numerical range is satisfied, the reaction time can be shortened and the deuterium substitution rate can be increased.

In addition, the deuterium substitution rate of the compound may be improved by repeating the step b) two or more times.

In step c), the methylene chloride layer is separated by extracting the second reactant with methylene chloride and water, and the separated methylene chloride layer is dried to obtain a compound of Formula 2.

In addition, the present invention relates to an organic light emitting diode comprising the deuterated compound for OLED in a light emitting layer.

The deuterated compound of the present invention can be applied to the light emitting layer of an organic light emitting diode to improve the life, stability and efficiency of a device.

Hereinafter, the present invention will be described in detail through examples and comparative examples. The following examples are only exemplified for the practice of the present invention, and the contents of the present invention are not limited by the following examples.

[Example 1] Compound of Formula 1

30 ml of 9H-carbazole and 7.5 mg of Pt / C were added to ₂ ml of D ₂ O and mixed through ultrasonic treatment for 5 minutes to prepare a first reactant (weight ratio of 9H-carbazole and Pt / C was 4: 1. ).

Hydrogen gas was added to the first reactant, and a second reactant was prepared by reacting at 160 ° C for 1 hour and 30 minutes using a microwave reactor (160W).

The second reactant was extracted with methylene chloride and water to separate the methylene chloride layer, and the separated methylene chloride layer was dried to obtain a compound of Formula 1.

The ¹ H NMR spectrum of the obtained compound was analyzed to confirm whether the compound of Formula 1 was produced, and the deuterium substitution rate of the prepared compound was 81%.

[Example 2] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that the reaction using a microwave reactor was performed twice.

1 shows a ¹ H NMR spectrum of the prepared compound, and the deuterium substitution rate of the prepared compound was 92.5%.

[Example 3] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that the reaction was performed at 80 ° C., and the deuterium substitution rate of the prepared compound was 26%.

[Example 4] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that the reaction was performed at 120 ° C., and the deuterium substitution rate of the prepared compound was 67%.

[Example 5] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that the reaction was performed at 180 ° C., and the deuterium substitution rate of the prepared compound was 31%.

[Example 6] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that 9H-carbazole 30mg and Pt / C 2mg were used (the weight ratio of 9H-carbazole and Pt / C is 15: 1), production The deuterium substitution rate of the compound was 36%.

[Example 7] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that 30 mg of 9H-carbazole and 3 mg of Pt / C were used (the weight ratio of 9H-carbazole and Pt / C is 10: 1). The deuterium substitution rate of the compound was 79%.

[Example 8] Compound of Formula 1

A compound of Formula 1 was prepared in the same manner as in Example 1, except that 30 mg of 9H-carbazole and 15 mg of Pt / C were used (weight ratio of 9H-carbazole and Pt / C is 2: 1). The deuterium substitution rate of the compound was 41%.

[Example 9] Compound of formula (2)

50 mg of 2-phenylpyridine and 12.5 mg of Pd / C were added to 2 ml of D ₂ O and mixed through ultrasonic treatment for 5 minutes to prepare a first reactant (weight ratio of 2-phenylpyridine to Pd / C is 4: 1. ).

Hydrogen gas was added to the first reactant, and a second reactant was prepared by reacting at 160 ° C. for 1 hour using a microwave reactor (160 W).

The second reactant was extracted with methylene chloride and water to separate the methylene chloride layer, and the separated methylene chloride layer was dried to obtain a compound of Formula 2.

2 shows a ¹ H NMR spectrum of the prepared compound, and the deuterium substitution rate of the prepared compound was 90%.

[Example 10] Compound of formula (2)

A compound of Formula 2 was prepared in the same manner as in Example 9, except that the reaction was performed at 80 ° C., and the deuterium substitution rate of the prepared compound was 10%.

[Example 11] Compound of Formula 2

A compound of Formula 2 was prepared in the same manner as in Example 9, except that the reaction was performed at 120 ° C., and the deuterium substitution rate of the prepared compound was 67%.

[Example 12] Compound of formula (2)

A compound of Formula 2 was prepared in the same manner as in Example 9, except that the reaction was performed at 180 ° C., and the deuterium substitution rate of the prepared compound was 38%.

[Example 13] Compound of Formula 2

A compound of Formula 2 was prepared in the same manner as in Example 9, except that 2-phenylpyridine 50mg and Pd / C 4mg were used (weight ratio of 2-phenylpyridine and Pd / C is 12.5: 1), and production The deuterium substitution rate of the compound was 42%.

[Example 14] Compound of Formula 2

A compound of Formula 2 was prepared in the same manner as in Example 9, except that 50 mg of 2-phenylpyridine and 5 mg of Pd / C were used (the weight ratio of 2-phenylpyridine and Pd / C is 10: 1). The deuterium substitution rate of the compound was 62%.

[Example 15] Compound of formula (2)

A compound of Formula 2 was prepared in the same manner as in Example 9, except that 2-phenylpyridine 50mg and Pd / C 25mg were used (weight ratio of 2-phenylpyridine and Pd / C is 2: 1), and production The deuterium substitution rate of the compound was 41%.

Deuterium substitution rates of the compounds prepared from the examples are shown in the table below.

Reaction temperature
(℃) Reaction time
(h) 9H-carbazole or 2-phenylpyridine; And weight ratio of catalyst Deuterium substitution rate
(%) Example 1 160 1.5 4: 1 81 Example 2 160 1.5 4: 1 92.5 Example 3 80 1.5 4: 1 26 Example 4 120 1.5 4: 1 67 Example 5 180 1.5 4: 1 31 Example 6 160 1.5 15: 1 36 Example 7 160 1.5 10: 1 79 Example 8 160 1.5 2: 1 41 Example 9 160 One 4: 1 90 Example 10 80 One 4: 1 10 Example 11 120 One 4: 1 67 Example 12 180 One 4: 1 38 Example 13 160 One 12.5: 1 42 Example 14 160 One 10: 1 62 Example 15 160 One 2: 1 41

As can be seen from the above table, when the reaction temperature is 100 to 160 ° C (Examples 1, 2, 4, 9 and 11), the deuterium substitution rate of the compound prepared during a short reaction time (30 minutes to 2 hours) is increased. You can. On the other hand, when the reaction temperature is 80 ℃ and 180 ℃ (Examples 3, 5, 10, 12), it can be seen that the deuterium substitution rate is low.

Also 9H-carbazole or 2-phenylpyridine; And when the weight ratio of the catalyst is 3 to 10: 1 (Examples 1, 2, 7, 9, 14), it is possible to increase the deuterium substitution rate of the compound prepared for a short reaction time (30 minutes to 2 hours). On the other hand, when the weight ratio is outside the above numerical range (Examples 6, 8, 13, 15), it can be seen that the deuterium substitution rate is low.

Claims (6)

delete a) preparing a first reactant by mixing D ₂ O, the compound of Formula 3, and a catalyst;
b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And
c) extracting the second reactant to obtain a compound of Formula 1 below;
In the method for producing a deuterated compound for OLED comprising a,
Step a) is
0.5 to 10 parts by weight of the compound of Formula 3 and 0.1 to 1 parts by weight of the catalyst are used relative to 100 parts by weight of D ₂ O,
The compound of Formula 3 and the catalyst are used in a weight ratio of 3 to 10: 1,
The b) method of manufacturing a deuterated compound for OLED, characterized in that is performed for 30 minutes to 2 hours at 100 ~ 160 ℃.
[Formula 3]

[Formula 1]

a) preparing a first reactant by mixing D ₂ O, a compound of Formula 4, and a catalyst;
b) adding hydrogen gas to the first reactant and reacting it using a microwave reactor to prepare a second reactant; And
c) extracting the second reactant to obtain a compound of Formula 2 below;
In the method for producing a deuterated compound for OLED comprising a,
Step a) is
0.5 to 10 parts by weight of the compound of Formula 4 and 0.1 to 1 part by weight of catalyst are used relative to 100 parts by weight of D ₂ O,
The compound of Formula 4 and the catalyst are used in a weight ratio of 3 to 10: 1,
The step b) is a method of manufacturing a deuterated compound for OLED, characterized in that is performed for 30 minutes to 2 hours at 100 ~ 160 ℃.
[Formula 4]

[Formula 2]

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