KR20230093979A - Organic compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more specifically, to an organic compound having excellent heat resistance, carrier transport ability, and luminescence ability, and an organic electroluminescent device including the organic compound in one or more organic material layers to have improved luminous efficiency, driving voltage, and lifespan characteristics. The organic compound is represented by chemical formula 1 or chemical formula 2.

Description

Organic compound and organic electroluminescent device using the same {ORGANIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, to a novel compound having excellent heat resistance, carrier transport ability, and light emitting ability, and by including the same in one or more organic material layers, luminous efficiency, driving voltage, lifespan, etc. It relates to an organic electroluminescent device with improved characteristics.

When a voltage is applied between the two electrodes of the organic electroluminescent device (hereinafter referred to as 'organic EL device'), holes are injected from the anode and electrons are injected into the organic material layer from the cathode. When the injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. At this time, the material used as the organic material layer may be classified according to its function into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like.

Materials for forming the light emitting layer of the organic EL device may be classified into blue, green, and red light emitting materials according to the light emitting color. In addition, yellow and orange light emitting materials are also used as light emitting materials for implementing better natural colors. In addition, in order to increase color purity and increase light emitting efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminous efficiency up to 4 times compared to fluorescence, so attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Until now, hole injection layer, hole transport layer. NPB, BCP, Alq ₃ and the like are widely known as hole blocking layers and electron transport layers, and anthracene derivatives have been reported as fluorescent dopant/host materials for light emitting materials. In particular, phosphorescent materials that have a great advantage in terms of efficiency improvement among light emitting materials include metal complex compounds containing Ir such as Firpic, Ir(ppy) ₃ , and (acac)Ir(btp) ₂ as blue, green, and red dopant materials. is being used as So far, CBP has shown excellent properties as a phosphorescent host material.

However, conventional organic layer materials are advantageous in terms of light emitting properties, but have low glass transition temperatures and very poor thermal stability, so they are not satisfactory in terms of lifespan in organic EL devices. Therefore, there is a demand for the development of organic layer materials with excellent performance.

Republic of Korea Patent Publication No. 10-2016-126862

An object of the present invention is an organic layer material of an organic electroluminescent device, specifically a light emitting layer material, a lifespan improvement layer material, a light emitting auxiliary layer material, an electron transport auxiliary layer material, and / or It is to provide a novel compound that can be used as an electron transport layer material or the like.

Another object of the present invention is to provide an organic electroluminescent device having a low driving voltage, high luminous efficiency, and improved lifespan, including the novel compound described above.

In order to achieve the above object, the present invention provides a compound represented by Formula 1 or 2 below:

(In Chemical Formulas 1 and 2,

n1 and n2 are each an integer from 0 to 4;

L ₁ and L ₂ are each independently a single bond or selected from the group consisting of a C ₆ ~ C ₂₄ arylene group and a heteroarylene group having 3 to 24 nuclear atoms;

Sub ₁ and Sub ₂ are each a substituent represented by Formula 3 below,

In Formula 3,

Z ₁ to Z ₃ are the same as or different from each other, and are each independently N or C(R ₆ ), provided that at least one of Z ₁ to Z ₃ is N, wherein, when C(R ₆ ) is plural, a plurality of R ₆ are the same as or different from each other;

Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently hydrogen, deuterium, tritium, C ₂ ~C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, nucleus Heterocycloalkyl group having 3 to 40 atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~C ₆₀ aryloxy group, C ₁ ~C ₄₀ alkylsilyl group, C ₆ ~C ₆₀ arylsilyl group, C ₁ ~C ₄₀ alkylboron group, C ₆ ~C ₆₀ arylboron group, C ₆ It is selected from the group consisting of ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ arylamine group,

a is an integer from 0 to 3;

b is an integer from 0 to 4;

c is an integer from 0 to 5;

d is an integer from 0 to 4;

e is an integer from 0 to 4;

R ₁ to R ₆ are the same as or different from each other, and are each independently hydrogen, deuterium, tritium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₁ ~C ₄₀ alkyl group, C ₆ ~C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ selected from the group consisting of arylamine group, or condensation by combining with adjacent groups form a ring,

Arylene and heteroarylene groups of L ₁ and L ₂ , Ar ₁ and Ar ₂ of alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, alkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, An alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group, and an arylamine group, an alkenyl group of R ₁ to R ₆ , an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, An alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group, an arylamine group, and a condensed ring Each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C It is substituted or unsubstituted with one or more substituents selected from the group consisting of a ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group, and when the substituents are plural, they are the same as or different from each other).

In addition, the present invention is an anode; cathode; It includes one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers includes the above-mentioned compound.

The compound of the present invention can be used as a material for an organic material layer of an organic electroluminescent device because it has excellent electron injection and transport ability, light emitting ability, thermal stability, and electrochemical stability. In particular, when the compound of the present invention is used as at least one of a host material, an electron transport layer material, and an electron transport auxiliary layer material, an organic electroluminescent device having low driving voltage, high efficiency, and long lifespan characteristics can be manufactured compared to conventional materials, Furthermore, a full color display panel with improved performance and lifespan can be manufactured.

Effects according to the present invention are not limited by the contents exemplified above, and more diverse effects are included in the present specification.

1 is a schematic cross-sectional view of an organic electroluminescent device according to a first embodiment of the present invention.
2 is a schematic cross-sectional view of an organic electroluminescent device according to a second embodiment of the present invention.
3 is a schematic cross-sectional view of an organic electroluminescent device according to a third embodiment of the present invention.

Hereinafter, the present invention will be described.

<New organic compounds>

The compound according to the present invention has a nitrogen-containing heteroaromatic ring group at boron position 10 of the dibenzo[b,e][1,4]oxaborinine moiety. It includes a basic structure formed by introduction directly or through a linker group, or a phenyl group is introduced at boron position 10 of the dibenzo[b,e][1,4]oxaborinine moiety, and carbon positions 1 to 4 A compound having a basic structure in which a nitrogen (N)-containing heteroaromatic ring group is introduced directly or through a linker group at any carbon position, and is represented by Formula 1 or 2 above. The compound of the present invention is excellent in electron injection and transport ability, electrochemical stability, heat resistance, etc., and can be used as an electron transport layer material or an electron transport auxiliary layer material that can improve the high efficiency, long lifespan, and driving voltage characteristics of an organic electroluminescent device. there is. Here, the carbon/boron/oxygen position number of the dibenzo[b,e][1,4]oxaborinine moiety can be represented as follows.

Specifically, in the compound represented by Formula 1 or 2, the dibenzo[b,e][1,4]oxaborinine moiety has electron acceptor properties with weak electron absorption. On the other hand, a nitrogen-containing heteroaromatic ring group (eg, triazine ring group, pyrimidine ring group, etc.) is an electron withdrawing group (EWG) having high electron absorption. Therefore, when a nitrogen-containing heteroaromatic ring group is introduced directly or through a linker group (eg, an arylene group) to the dibenzo[b,e][1,4]oxaborinine moiety, it has fast electron transfer ability. Therefore, when the compound of the present invention is used as an electron transport layer material or an electron transport auxiliary layer material of an organic light emitting device, current flow and current density are improved, thereby reducing the driving voltage of the device and increasing current efficiency.

In addition, the dibenzo [b, e] [1,4] oxaborinine moiety has a very high triplet (T1) energy compared to arylene moieties (eg, naphthalene, anthracene, etc.), as well as nitrogen-containing Depending on the bonding position and shape of the linker group (eg, arylene group, etc.) located between the heteroaromatic ring group, it is possible to maintain a structure having a strong steric hindrance, thereby maintaining a high T1 energy level. At this time, the break of pi-conjugation is controlled with a linker group (eg, arylene group, etc.) between the dibenzo[b,e][1,4]oxaborinine moiety and the nitrogen-containing heteroaromatic ring group, thereby increasing T1 of the compound. By increasing the energy, the characteristics of the element can be improved. In particular, when the length of the linker group is shortened, conjugation is further severed by using the substituent introduced into the nitrogen-containing heteroaromatic ring group and the strong steric hindrance of the dibenzo[b,e][1,4]oxaborinine moiety. By increasing it, a high T1 energy can be maintained. The compound of the present invention can prevent excitons generated in the light emitting layer from diffusing (moving) to an organic material layer (eg, an electron transport layer, an electron injection layer, etc.) adjacent to the light emitting layer. Therefore, when a separate organic material layer (hereinafter referred to as an 'electron transport auxiliary layer') located between the light emitting layer and the electron transport layer is formed using the compound of the present invention, since diffusion of excitons is prevented by the compound, the electron Unlike a conventional organic light emitting device that does not include a transport auxiliary layer, the number of excitons contributing to light emission in the light emitting layer is substantially increased, so that the light emitting efficiency of the device can be improved. In addition, when the compound of the present invention is used as an electron transport auxiliary layer material, electrons can be rapidly transferred from the electron transport layer to the light emitting layer due to high current density and fast electron mobility, and further, due to the high T1 energy level, non-radiative recombination (non-radiative recombination) radiative recombination) can be prevented to improve the efficiency and lifetime of the device.

In addition, since the compound of the present invention has a plate-like structure in which the dibenzo[b,e][1,4]oxaborinine moiety has a plate-like structure compared to the arylene moiety (eg, naphthalene, anthracene, etc.), it is difficult to stack during deposition of the device. Through this, excellent charge mobility can be maintained during device driving, and electron injection and transport properties can be improved. In addition, the compound of the present invention controls the intramolecular conjugation region by introducing an arylene group having various bond types to the dibenzo[b,e][1,4]oxaborinine moiety and/or the nitrogen-containing heteroaromatic ring group. Alternatively, electron injection and transport properties may be improved by applying strong steric hindrance to improve charge mobility. Therefore, when the compound represented by Formula 1 or 2 is applied as a material for an electron transport layer or an electron transport auxiliary layer of an organic electroluminescent device, electrons can be smoothly transferred from the cathode (or electron injection layer) to the light emitting layer, and as a result The driving voltage of the device is lowered, and high efficiency and long lifespan characteristics can be implemented.

As described above, the compound represented by Formula 1 or 2 according to the present invention has excellent electron injection and transport ability, thermal stability, and electrochemical stability. Therefore, the compound of the present invention is an organic material layer of an organic electroluminescent device, preferably a light emitting layer material (a blue, green and/or red phosphorescent host material), an electron transport layer/injection layer material, an electron transport auxiliary layer material, and a hole transport layer/injection layer. It can be used as a material, a light emitting auxiliary layer material, a lifespan improving layer material, and more preferably an electron transport layer material and an electron transport auxiliary layer material. Performance and lifetime characteristics of the organic electroluminescent device including the compound of the present invention can be greatly improved, and the performance of a full-color organic light emitting panel to which the organic electroluminescent device is applied can also be maximized.

In the compound represented by Formula 1 or 2 according to the present invention, n1 and n2 may each be an integer of 0 to 4, and specifically, each may be an integer of 0 to 3.

Here, when n1 (or n2) is 0, L ₁ (or L ₂ ) is directly bonded (single bond). On the other hand, when n1 (or n2) is an integer of 1 to 4, L ₁ (or L ₂ ) is a divalent linker group, a C ₆ ~ C ₂₄ arylene group and a heteroaryl group having 5 to 24 nuclear atoms. It is selected from the group consisting of an ene group, specifically, it may be selected from the group consisting of a C ₆ ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms.

The arylene group and heteroarylene group of L ₁ and L ₂ are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl Substituted or unsubstituted with one or more substituents selected from the group consisting of a boron group, a C ₆ ~ C ₆₀ arylphosphine group, a C ₆ ~ C ₆₀ arylphosphine oxide group, and a C ₆ ~ C ₆₀ arylamine group, and specifically independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, nucleus It may be unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocycloalkyl group having 3 to 40 atoms, a C ₆ ~C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms. In this case, when the substituents are plural, they are the same as or different from each other.

According to one example, the L ₁ and L ₂ may each be a direct bond or selected from the group consisting of a phenylene group, a biphenylene group, a naphthalene group, and a terphenylene group. At this time, the hydrogen of the phenylene group, biphenylene group, naphthalene group and terphenylene group is deuterium (D), halogen, cyano group, nitro group, C ₁ ~ C ₁₂ alkyl group, C ₆ ~ C ₁₀ aryl group, and It may be substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups having 5 to 10 nuclear atoms.

Depending on L ₁ and L ₂ , the compound represented by Formula 1 or 2 may be a compound represented by Formula 4 or 5, but is not limited thereto.

In Formulas 4 and 5,

n1, n2, Sub ₁ , Sub ₂ , a, b, c, d, e, R ₁ to R ₅ are each as defined in Formula 1 above;

f is an integer from 0 to 4;

One or more R ₇ are the same as or different from each other, and are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl It is selected from the group consisting of a boron group, a C ₆ ~ C ₆₀ arylphosphine group, a C ₆ ~ C ₆₀ arylphosphine oxide group, and a C ₆ ~ C ₆₀ arylamine group, and specifically, each independently deuterium, halogen, cyano No group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₆ ~ C ₆₀ It may be selected from the group consisting of an aryl group, and a heteroaryl group having 5 to 60 nuclear atoms, more specifically deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, 3 to 20 nuclear atoms heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, and nuclear atoms It may be selected from the group consisting of 5 to 30 heteroaryl groups.

및

는 각각 직접 결합이거나, 또는 하기 링커기 L-1 내지 L-14로 이루어진 군에서 선택된 것일 수 있다. 다만, 이에 한정되지 않는다.According to one example, in Chemical Formulas 4 and 5,

and

Each may be a direct bond or selected from the group consisting of the following linker groups L-1 to L-14. However, it is not limited thereto.

In the linker groups L-1 to L-14,

* means a site connected to Formula 4 or 5,

f and R ₇ are as defined in formulas 4 and 5, respectively.

In the compound represented by Formula 1 or 2 according to the present invention, Sub ₁ and Sub ₂ are substituents represented by Formula 3, respectively, and are a kind of nitrogen (N)-containing heteroaromatic ring.

In the substituent represented by Formula 3, Z ₁ to Z ₃ are the same as or different from each other, and are each independently N or C(R ₆ ), provided that at least one of Z ₁ to Z ₃ is N. At this time, when C(R ₆ ) is plural, the plurality of R ₆ are the same as or different from each other.

Here, one or more R ₆ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, tritium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alky Nyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, It is selected from the group consisting of a C ₆ ~ C ₆₀ arylboron group, a C ₆ ~ C ₆₀ arylphosphine group, a C ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group, or an adjacent group to form a condensed ring, specifically hydrogen, deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, and heteroaryl having 5 to 60 nuclear atoms, each independently It may be selected from the group consisting of groups.

An alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group of R ₆ , Arylphosphine group, arylphosphine oxide group, arylamine group and condensed ring are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₁ ~C ₄₀ alkyl group, C ₆ ~C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups and, specifically, each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cyclo It may be unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms. In this case, when the substituents are plural, they are the same as or different from each other.

According to one example, the substituent represented by Chemical Formula 3 may be a substituent selected from the group consisting of the following substituents S1-1 to S1-3, respectively.

In the above substituents S1-1 to S1-3,

* means a site connected to Formula 1,

Ar ₁ , Ar ₂ , and R ₆ are each as defined in Chemical Formula 3 above.

In the substituent represented by Formula 3, Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently selected from the group consisting of a C ₆ ~ C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and specifically Each independently selected from the group consisting of a C ₆ ~ C ₃₀ aryl group and a heteroaryl group having 5 to 30 nuclear atoms.

An alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, and an aryl of Ar ₁ and Ar ₂ The boron group, the arylphosphine group, the arylphosphine oxide group, and the arylamine group are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₁ ~C ₄₀ alkyl group, C ₆ ~C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups and, specifically, each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cyclo It may be unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms. In this case, when the substituents are plural, they are the same as or different from each other.

According to one example, in the substituent represented by Formula 3, Ar ₁ and Ar ₂ may be the same as or different from each other, and each independently may be a substituent selected from the group consisting of the following substituents S2-1 to S2-12.

In the substituents S2-1 to S2-12,

R ₈ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl It is selected from the group consisting of a boron group, a C ₆ ~ C ₆₀ arylphosphine group, a C ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group, and specifically, each independently hydrogen, deuterium, halogen , A cyano group, a C ₁ ~ C ₄₀ alkyl group, a C ₆ ~ C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.

Hydrogen of the substituents S2-1 to S2-12 is deuterium (D), halogen, cyano group, nitro group, C ₁ ~ C ₁₂ alkyl group, C ₆ ~ C ₁₀ aryl group, and 5 to 10 nuclear atoms It may be substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups.

In the compound represented by Formula 1 or 2, a is an integer from 0 to 3, b is an integer from 0 to 4, c is an integer from 0 to 5, d is an integer from 0 to 4, and e is 0 is an integer from 4 to 4.

In addition, R ₁ to R ₅ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, tritium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group , C ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C It is selected from the group consisting of _{a 6} ~C ₆₀ arylboron group, a C ₆ ~C ₆₀ arylphosphine group, a C ₆ ~C ₆₀ arylphosphine oxide group, and a C ₆ ~C ₆₀ arylamine group, or an adjacent group Combined to form a condensed ring, specifically, selected from the group consisting of deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, and heteroaryl group having 5 to 60 nuclear atoms. can

Here, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group of R ₁ to R ₆ , An aryl boron group, an aryl phosphine group, an aryl phosphine oxide group, an aryl amine group, and a condensed ring are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms , C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group , C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ arylamine group selected from the group consisting of one or more substituents substituted or unsubstituted with, specifically, each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, and 5 to 60 nuclear atoms substituted with one or more substituents selected from the group consisting of, or unsubstituted can be redeemed In this case, when the substituents are plural, they are the same as or different from each other.

Depending on the above-mentioned L ₁ , L ₂ , and the substituent of Formula 3, the compound represented by Formula 1 or 2 may be a compound represented by any one of Formulas 6 to 11, but is not limited thereto.

In Formulas 6 to 11,

n1, n2, a, b, c, d, e, R ₁ to R ₅ , Ar ₁ and Ar ₂ are each as defined in Formula 1 above;

f is an integer from 0 to 4;

R ₇ is deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C It is selected from the group consisting of ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ arylamine group, specifically deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.

In Chemical Formulas 6 to 8, at least one of a plurality of R ₁ to a plurality of R ₃ , a plurality of R ₇ , Ar ₁ and Ar ₂ may be deuterium (D), and specifically, at least one of a plurality of R ₇ It may be deuterium. Meanwhile, in Chemical Formulas 9 to 11, at least one of a plurality of R ₄ to a plurality of R ₅ , a plurality of R ₇ , Ar ₁ and Ar ₂ may be deuterium (D), and at least one of a plurality of R ₇ It may be deuterium.

According to one example, the compound represented by Formula 1 or 2 may include at least one deuterium (D), and in this case, the deuterium substitution rate of the compound may be greater than 0% to 100%, specifically 1 to 100%. .

The compound represented by Formula 1 or 2 according to the present invention described above may be further embodied in the following compounds 1 to 400, but is not limited thereto.

In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, "alkenyl" refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are N, O, S or a heteroatom such as Se. Examples of such heterocycloalkyl include morpholine, piperazine, and the like, but are not limited thereto.

In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, "heteroaryl" means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and furthermore, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. can include Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means an aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

In the present invention, "alkylsilyl" means a silyl substituted with an alkyl having 1 to 40 carbon atoms, and includes mono- as well as di- and tri-alkylsilyl. Also, "arylsilyl" means a silyl substituted with an aryl having 5 to 60 carbon atoms, and includes polyarylsilyl such as mono- as well as di- and tri-arylsilyl.

In the present invention, "alkyl boron group" refers to a boron group substituted with an alkyl having 1 to 40 carbon atoms, and "aryl boron group" refers to a boron group substituted with an aryl having 6 to 60 carbon atoms.

In the present invention, "alkylphosphinyl group" means a phosphine group substituted with an alkyl having 1 to 40 carbon atoms, and includes mono- as well as di-alkylphosphinyl groups. In the present invention, "arylphosphinyl group" means a phosphine group substituted with a monoaryl or diaryl having 6 to 60 carbon atoms, and includes mono- as well as di-arylphosphinyl groups.

In the present invention, "arylamine" means an amine substituted with an aryl having 6 to 60 carbon atoms, and includes mono- as well as di-arylamines.

In the present invention, "heteroarylamine" means an amine substituted with heteroaryl having 5 to 60 nuclear atoms, and includes mono- as well as di-heteroarylamine.

In the present invention, (aryl)(heteroaryl)amine means an amine substituted with an aryl having 6 to 60 carbon atoms and a heteroaryl having 5 to 60 nuclear atoms.

In the present invention, "condensed ring" is a condensed aliphatic ring having 3 to 40 carbon atoms, a condensed aromatic ring having 6 to 60 carbon atoms, a condensed heteroaliphatic ring having 3 to 60 nuclear atoms, a condensed heteroaromatic ring having 5 to 60 nuclear atoms, It means a spiro ring having 3 to 60 carbon atoms or a combination thereof.

<Organic electroluminescent device>

Meanwhile, the present invention provides an organic electroluminescent device (hereinafter, 'organic EL device') including the compound represented by Formula 1 or 2 above.

Specifically, as shown in FIGS. 1 to 3, the organic electroluminescent device according to the present invention includes an anode 100, a cathode 200, and interposed between the anode and the cathode. It includes one or more organic material layers 300, and at least one of the one or more organic material layers includes the compound represented by Chemical Formula 1 or 2. At this time, the above compounds may be used alone or in combination of two or more.

The one or more organic material layers 300 may include at least one of a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340, and an electron injection layer 350, Optionally, an electron transport auxiliary layer 360 may be additionally included. At this time, at least one organic material layer 300 includes the compound represented by Formula 1 or 2 above. Specifically, the organic material layer including the compound of Chemical Formula 1 or 2 may be at least one of the light emitting layer 330 , the electron transport layer 340 , and the electron transport auxiliary layer 360 .

According to one example, the one or more organic material layers include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and optionally may further include an electron transport auxiliary layer. The electron transport layer includes the compound represented by Formula 1 or 2 above. At this time, the compound represented by Formula 1 or 2 is included in the organic electroluminescent device as an electron transport layer material. In such an organic electroluminescent device, electrons can be easily injected from the cathode or the electron injection layer to the electron transport layer and can move quickly from the electron transport layer to the light emitting layer because of the compound of Formula 1 or 2, so that holes and electrons in the light emitting layer can be easily injected. high bonding strength. Therefore, the organic electroluminescent device of the present invention is excellent in luminous efficiency, power efficiency, luminance, and the like. In addition, the compound of Chemical Formula 1 or 2 has excellent thermal stability and electrochemical stability, and thus can improve the performance of an organic electroluminescent device.

The compound represented by Chemical Formula 1 or 2 may be used alone or mixed with an electron transport layer material known in the art.

In the present invention, the electron transport layer material that can be mixed with the compound of Formula 1 or 2 includes an electron transport material commonly known in the art. Non-limiting examples of usable electron transport materials include oxazole-based compounds, isoxazole-based compounds, triazole-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene ( perylene)-based compounds, aluminum complexes (eg Alq _3, tris(8-quinolinolato)-aluminium), gallium complexes (eg Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)), and the like. These may be used alone or in combination of two or more.

In the present invention, when the compound of Formula 1 or 2 and the electron transport layer material are mixed, the mixing ratio thereof is not particularly limited and may be appropriately adjusted within a range known in the art.

According to another example, the one or more organic material layers include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and the electron transport auxiliary layer is represented by Formula 1 or 2 contains a compound At this time, the compound represented by Formula 1 or 2 is included in the organic electroluminescent device as an electron transport auxiliary layer material. In this case, the compound of Formula 1 or 2 has high triplet energy. For this reason, when the compound of Chemical Formula 1 or 2 is included as an electron transport auxiliary layer material, the efficiency of the organic EL device may be increased due to a triplet-triplet fusion (TTF) effect. In addition, the compound of Chemical Formula 1 or 2 can prevent diffusion of excitons or holes generated in the light emitting layer to the electron transport layer adjacent to the light emitting layer. Accordingly, the number of excitons contributing to light emission in the light emitting layer is increased, so that the light emitting efficiency of the device can be improved, and the lifespan of the device can be effectively increased by improving durability and stability of the device.

The compound of Chemical Formula 1 or 2 may be used alone or may be mixed with an electron transport layer auxiliary layer material known in the art.

In the present invention, the auxiliary electron transport layer material that can be mixed with the compound of Formula 1 or 2 includes electron transport materials commonly known in the art, such as oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives. (eg, BCP), heterocyclic derivatives containing nitrogen, and the like, but are not limited thereto.

The structure of the above-described organic electroluminescent device of the present invention is not particularly limited, but, for example, an anode 100, one or more organic material layers 300, and a cathode 200 may be sequentially stacked on a substrate (FIG. 1 to FIG. see 3). In addition, although not shown, an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic material layer.

According to one example, the organic electroluminescent device, as shown in Figure 1, on a substrate, the anode 100, the hole injection layer 310, the hole transport layer 320, the light emitting layer 330, the electron transport layer 340 and the cathode 200 may have a sequentially stacked structure. Optionally, as shown in FIG. 2 , an electron injection layer 350 may be positioned between the electron transport layer 340 and the cathode 200 . In addition, an electron transport auxiliary layer 360 may be positioned between the light emitting layer 330 and the electron transport layer 340 (see FIG. 3 ).

In the organic electroluminescent device of the present invention, at least one of the organic material layers 300 (eg, the light emitting layer 330, the electron transport layer 340, or the electron transport auxiliary layer 360) includes a compound represented by Formula 1 or 2 above. Except for, it can be manufactured by forming an organic material layer and an electrode with materials and methods known in the art.

The organic layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution application method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

Substrates usable in the present invention are not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

In addition, examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline; and carbon black, but is not limited thereto.

In addition, examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin, or lead or alloys thereof; and multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

In addition, the hole injection layer, the hole transport layer, the light emitting layer, and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only to illustrate the present invention, and the present invention is not limited by the following examples.

[ preparation example 1] Synthesis of Compound A-1

[ preparation example 1-1] Synthesis of Compound A-1-iii

4-chlorophenol 50g (388.9mmol, 1eq), fluorobenzene 39.2g (408.4mmol, 1.05eq), and Cs ₂ CO ₃ 253.4g (777.8mmol, 2eq) were put in DMAc 1000ml and heated under reflux for 3 hours. After completion of the reaction, the reaction solution was filtered to remove the white salt, and the filtrate was deactivated with a sufficient amount of water, and then the solution was transferred to a separatory funnel and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-1-iii (70 g, yield 88%).

[Preparation Example 1-2] Synthesis of Compound A-1-ii

After putting 70g (342.0mmol, 1eq) of 1-chloro-4-phenoxybenzene in 1050 ml of MC, cooling to -30 ° C and stirring, slowly adding 171.4g (684.1mmol, 2eq) of BBr ₃ dropwise, then raising the temperature to room temperature. Stir for 1 hour. After completion of the reaction, water was slowly added dropwise to the reaction solution to deactivate it, and then the solution was transferred to a separatory funnel to extract an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-1-ii (60 g, yield 60%).

[Preparation Example 1-3] Synthesis of Compound A-1-i

60g (204.5mmol, 1eq) of 10-bromo-2-chloro-10H-dibenzo[b,e][1,4]oxaborinine was added to 900ml of anhydrous THF, cooled to -78 ℃, and 2.5M n- 90ml (225.0mmol, 1.1eq) of BuLi was slowly added dropwise and stirred for 30 minutes. Here, 26.2g (214.8mmol, 1.05eq) of phenylboronic acid was added and stirred for 2 hours while slowly raising the temperature to room temperature. After inactivation by slowly adding an aqueous hydrochloric acid dropwise to the reaction mixture, the resulting precipitate was filtered off. Thereafter, the filtrate was transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-1-i (32.7 g, yield 55%).

Mass : [(M+H) ⁺ ] : 290.55

NMR ( ¹ H): σ = 7.71-7.75 (3H, m), 7.37.-7.35 (5H, m), 7.30 (1H, s), 7.07 (1H, t), 7.00 (1H, d), 6.94 ( 1H, d)

[Preparation Example 1-4] Synthesis of Compound A-1

2-chloro-10-phenyl-10H-dibenzo[b,e][1,4]oxaborinine 32.7g (112.5mmol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 34.3g(135.1mmol, 1.2eq), Pd ₂ (dba) ₃ 5.15g(5.6mmol, 0.05eq), Xphos 5.37g(11.3mmol) , 0.1eq), and 22.1g (225.1mmol, 2eq) of KOAc were added to 500ml of 1,4-dioxane and stirred under reflux for 4 hours. After completion of the reaction, it was deactivated with a sufficient amount of water, transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. The resulting solid was filtered to remove the solution, and then dried in an oven. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-1 (28g, yield 65%).

[Preparation Example 2] Synthesis of Compound A-2

[Preparation Example 2-1] Synthesis of Compound A-2-iii

3-chlorophenol 50g (388.9mmol, 1eq), fluorobenzene 39.2g (408.4mmol, 1.05eq), and Cs ₂ CO ₃ 253.4g (777.8mmol, 2eq) were added to DMAc 1000ml and heated under reflux for 3 hours. After completion of the reaction, the reaction solution was filtered to remove the white salt, and the filtrate was deactivated with a sufficient amount of water, and then the solution was transferred to a separatory funnel and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-2-iii (71.6 g, yield 90%).

[Preparation Example 2-2] Synthesis of Compound A-2-ii

71.6g (349.9mmol, 1eq) of 1-chloro-3-phenoxybenzene was added to 1070 ml of MC, cooled to -30 ° C and stirred, and then 175.3g (699.7mmol, 2eq) of BBr ₃ was slowly added dropwise thereto, followed by room temperature. The temperature was raised and stirred for 1 hour. After completion of the reaction, water was slowly added dropwise to the reaction solution to deactivate it, and then the solution was transferred to a separatory funnel to extract an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-2-ii (56.4 g, yield 55%).

[Preparation Example 2-3] Synthesis of Compound A-2-i

56.4g (192.3mmol, 1eq) of 10-bromo-3-chloro-10H-dibenzo[b,e][1,4]oxaborinine was added to 850ml of anhydrous THF, cooled to -78 °C, and 2.5M n at the same temperature. -BuLi 84.6ml (211.5mmol, 1.1eq) was slowly added dropwise and stirred for 30 minutes. Here, 24.6g (201.9mmol, 1.05eq) of phenylboronic acid was added and stirred for 2 hours while slowly raising the temperature to room temperature. After inactivation by slowly adding an aqueous hydrochloric acid dropwise to the reaction mixture, the resulting precipitate was filtered off. Next, the filtrate was transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-2-i (32.4 g, yield 58%).

Mass : [(M+H) ⁺ ] : 290.55

NMR ( ¹ H): σ = 7.75-7.71 (3H, m), 7.65 (1H, d), 7.37-7.34 (5H, m), 7.14 (1H, d), 7.07 (1H, t), 7.00 (1H , d)

[Preparation Example 2-4] Synthesis of Compound A-2

3-chloro-10-phenyl-10H-dibenzo[b,e][1,4]oxaborinine 32.4g (111.5mmol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 34.0g(133.8mmol, 1.2eq), Pd ₂ (dba) ₃ 5.11g(5.6mmol, 0.05eq), Xphos 5.32g(11.2mmol) , 0.1eq), and 21.9g (223.0mmol, 2eq) of KOAc were added to 500ml of 1,4-dioxane and stirred under reflux for 4 hours. After completion of the reaction, it was deactivated with a sufficient amount of water, transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. The resulting solid was filtered to remove the solution, and then dried in an oven. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-2 (26.8 g, yield 63%).

[Preparation Example 3] Synthesis of Compound A-3

[Preparation Example 3-1] Synthesis of Compound A-3-iii

50g (388.9mmol, 1eq) of 2-chlorophenol, 39.2g (408.4mmol, 1.05eq) of fluorobenzene, and _253.4g (777.8mmol, 2eq) of Cs ₂ CO 3 were added to 1000ml of DMAc and heated under reflux for 3 hours. After completion of the reaction, the reaction solution was filtered to remove the white salt, and the filtrate was deactivated with a sufficient amount of water, and then the solution was transferred to a separatory funnel and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-3-iii (67.6 g, yield 85%).

[Preparation Example 3-2] Synthesis of Compound A-3-ii

After putting 67.7g (330.3mmol, 1eq) of 1-chloro-2-phenoxybenzene in 1000 ml of MC, cooling to -30 ° C and stirring, slowly adding 165.5g (660.6mmol, 2eq) of BBr ₃ dropwise, then raising the temperature to room temperature. Stir for 1 hour. After completion of the reaction, water was slowly added dropwise to the reaction solution to deactivate it, and then the solution was transferred to a separatory funnel to extract an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-3-ii (49.4 g, yield 51%).

[Preparation Example 3-3] Synthesis of Compound A-3-i

49.4g (168.4mmol, 1eq) of 10-bromo-4-chloro-10H-dibenzo[b,e][1,4]oxaborinine was added to 700ml of anhydrous THF, cooled to -78 ℃, and then diluted to 2.5M n at the same temperature. -BuLi 74.1ml (1825.2mol, 1.1eq) was slowly added dropwise and stirred for 30 minutes. Here, 21.6g (176.8mmol, 1.05eq) of phenylboronic acid was added and stirred for 2 hours while slowly raising the temperature to room temperature. After inactivation by slowly adding an aqueous hydrochloric acid dropwise to the reaction mixture, the resulting precipitate was filtered off. Next, the filtrate was transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-3-i (26.4 g, yield 54%).

Mass : [(M+H) ⁺ ] : 290.55

NMR ( ¹ H): σ = 7.75-7.71 (3H, m), 7.59 (1H, d), 7.38-7.35 (5H, m), 7.07 (1H, d), 7.00 (2H, d)

[Preparation Example 3-4] Synthesis of Compound A-3

4-chloro-10-phenyl-10H-dibenzo[b,e][1,4]oxaborinine 26.4g (90.9mmol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 27.7g(109.0mmol, 1.2eq), Pd ₂ (dba) ₃ 4.16g(4.5mmol, 0.05eq), Xphos 4.33g(9.1mmol) , 0.1eq), and 17.8g (181.7mmol, 2eq) of KOAc were added to 400ml of 1,4-dioxane and stirred under reflux for 4 hours. After completion of the reaction, it was deactivated with a sufficient amount of water, transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. After filtering the resulting solid to remove the solution, it was dried in an oven. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-3 (22.9g, yield 66%).

[Preparation Example 4] Synthesis of Compound A-4

[Preparation Example 4-1] Synthesis of Compound A-4-iii

Phenol 50g (531.3mmol, 1eq), fluorobenzene 53.6g (557.9mmol, 1.05eq) and Cs ₂ CO ₃ 346.2g (1062.6mmol, 2eq) were put in DMAc 1200ml and heated under reflux for 3 hours. After completion of the reaction, the reaction solution was filtered to remove the white salt, and the filtrate was deactivated with a sufficient amount of water, and then the solution was transferred to a separatory funnel and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-4-iii (83.2 g, yield 92%).

[Preparation Example 4-2] Synthesis of Compound A-4-ii

83.2g (488.8mmol, 1eq) of oxydibenzene was put into 1250 ml of MC, cooled to -30 ° C and stirred, then 244.9g (977.6mmol, 2eq) of BBr ₃ was slowly added dropwise thereto, followed by raising the temperature to room temperature for 1 hour. Stir. After completion of the reaction, water was slowly added dropwise to the reaction solution to deactivate it, and then the solution was transferred to a separatory funnel to extract an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-4-ii (69.6 g, yield 55%).

[Preparation Example 4-3] Synthesis of Compound A-4-i

69.6g (268.6mmol, 1eq) of 10-bromo-10H-dibenzo[b,e][1,4]oxaborinine was added to 1000ml of anhydrous THF, cooled to -78 ℃, and then 118.3ml of 2.5M n-BuLi at the same temperature. (295.7mmol, 1.1eq) was slowly added dropwise and stirred for 30 minutes. Here, 44.1g (282.3mmol, 1.05eq) of (4-chlorophenyl)boronic acid was added and stirred for 2 hours while slowly raising the temperature to room temperature. After inactivation by slowly adding an aqueous hydrochloric acid dropwise to the reaction mixture, the resulting precipitate was filtered off. Next, the filtrate was transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-4-i (46.9 g, yield 60%).

Mass : [(M+H) ⁺ ] : 290.55

NMR ( ¹ H): σ = 7.71-7.69 (4H, m), 7.42 (2H, d), 7.35 (2H, d), 7.07 (2H, d), 7.00 (2H, d)

[Preparation Example 4-4] Synthesis of Compound A-4

10-(4-chlorophenyl)-10H-dibenzo[b,e][1,4]oxaborinine 46.9g (161.4mmol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 49.2g(193.7mmol, 1.2eq), Pd ₂ (dba) ₃ 7.39g(8.1mmol, 0.05eq), Xphos 7.7g(16.1mmol) , 0.1eq), and 31.7g (322.8mmol, 2eq) of KOAc were added to 700ml of 1,4-dioxane and stirred under reflux for 4 hours. After completion of the reaction, it was deactivated with a sufficient amount of water, transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. After filtering the resulting solid to remove the solution, it was dried in an oven. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-4 (43g, yield 69%).

[Preparation Example 5] Synthesis of Compound A-5

[Preparation Example 5-1] Synthesis of Compound A-5-iii

Phenol 50g (531.3mmol, 1eq), fluorobenzene 53.6g (557.9mmol, 1.05eq), Cs ₂ CO ₃ 346.2g (1062.6mmol, 2eq) were put in DMAc 1200ml and stirred under reflux for 3 hours. After completion of the reaction, the reaction solution was filtered to remove the white salt, and the filtrate was deactivated with a sufficient amount of water, and then the solution was transferred to a separatory funnel and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-5-iii (81.4g, yield 90%).

[Preparation Example 5-2] Synthesis of Compound A-5-ii

81.4g (478.2mmol, 1eq) of oxydibenzene was put into 1200 ml of MC, cooled to -30 ° C and stirred, then 239.6g (956.5mmol, 2eq) of BBr ₃ was slowly added dropwise thereto, followed by raising the temperature to room temperature for 1 hour. Stir. After completion of the reaction, water was slowly added dropwise to the reaction solution to deactivate it, and then the solution was transferred to a separatory funnel to extract an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-5-ii (61.9 g, yield 50%).

[Preparation Example 5-3] Synthesis of Compound A-5-i

69.6g (239.1mmol, 1eq) of 10-bromo-10H-dibenzo[b,e][1,4]oxaborinine was added to 1000ml of anhydrous THF, cooled to -78 ℃, and then 105.2ml of 2.5M n-BuLi at the same temperature. (263.0mmol, 1.1eq) was slowly added dropwise and stirred for 30 minutes. Here, 39.3g (251.0mmol, 1.05eq) of (3-chlorophenyl)boronic acid was added and stirred for 2 hours while slowly raising the temperature to room temperature. After inactivation by slowly adding an aqueous hydrochloric acid dropwise to the reaction mixture, the resulting precipitate was filtered off. Next, the filtrate was transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-5-i (39.6 g, yield 57%).

Mass : [(M+H) ⁺ ] : 290.55

NMR ( ¹ H): σ = 7.71 (2H, d), 7.63 (1H, s), 7.35-7.29 (5H, m), 7.07 (2H, d), 7.00 (2H, d)

[Preparation Example 5-4] Synthesis of Compound A-5

10-(3-chlorophenyl)-10H-dibenzo[b,e][1,4]oxaborinine 39.6g (136.3mmol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 41.5g(163.6mmol, 1.2eq), Pd ₂ (dba) ₃ 6.24g(6.8mmol, 0.05eq), Xphos 6.50g(13.6mmol) , 0.1eq), and 26.8g (272.6mmol, 2eq) of KOAc were added to 600ml of 1,4-dioxane and stirred under reflux for 4 hours. After completion of the reaction, it was deactivated with a sufficient amount of water, transferred to a separatory funnel, and the organic layer was extracted with methylene chloride. The resulting solid was filtered to remove the solution, and then dried in an oven. Thereafter, the organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain the target compound A-5 (34g, yield 65%).

[Synthesis Example 1] Synthesis of Compound 13

Compound A-5 synthesized in Preparation Example 5 {10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 22-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine 7.2g ( 20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O The mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 13 (10 g, yield 85%).

Mass : [(M+H) ⁺ ] : 563.47

[Synthesis Example 2] Synthesis of Compound 23

Compound A-5 synthesized in Preparation Example 5 {10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5- Triazine 9.7g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and H ₂ O It was added to 45ml and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 23 (10.8g, yield 81%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 3] Synthesis of Compound 26

Compound A-5 synthesized in Preparation Example 5 {10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 22-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine 8.1g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq) and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 26 (9.4g, yield 80%).

Mass : [(M+H) ⁺ ] : 563.47

[Synthesis Example 4] Synthesis of Compound 33

Compound A-4 synthesized in Preparation Example 4 {10-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5- Triazine 9.7g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and H ₂ O It was added to 45ml and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 33 (11.1 g, yield 83%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 5] Synthesis of Compound 39

Compound A-5 synthesized in Preparation Example 5 10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e][ 1,4]oxaborinine 8g (20.9mmol, 1eq), 2-(3'-bromo-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine 9.7g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O. The mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 39 (11.2 g, yield 84%).

Mass : [(M+H) ⁺ ] :

[Synthesis Example 6] Synthesis of Compound 46

Compound A-4 synthesized in Preparation Example 4 {10-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-(dibenzo[b,d]furan-4-yl )-1,3,5-triazine 9.1g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) 1, Into 120ml of 4-dioxane and 45ml of H ₂ O, the mixture was stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 46 (10.9 g, yield 80%).

Mass : [(M+H) ⁺ ] : 653.55

[Synthesis Example 7] Synthesis of Compound 57

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-3-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine 9.7g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and H ₂ O 45ml and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 57 (10.5 g, yield 78%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 8] Synthesis of Compound 63

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine 9.7g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml, and H ₂ O It was added to 45ml and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 63 (10.7 g, yield 80%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 9] Synthesis of Compound 72

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-3-yl)-4-(3'-bromo-[1,1'-biphenyl]-4- yl)-6-phenyl-1,3,5-triazine 11.3g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) into 120ml of 1,4-dioxane and 45ml of H ₂ O, followed by heating under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 72 (12.3 g, yield 82%).

Mass : [(M+H) ⁺ ] : 715.66

[Synthesis Example 10] Synthesis of Compound 96

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-3-yl)-4-(4-bromophenyl)-6-(dibenzo[b,d]furan- 4-yl)-1,3,5-triazine 11.6g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) into 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 96 (11.8 g, yield 77%).

Mass : [(M+H) ⁺ ] : 729.65

[Synthesis Example 11] Synthesis of Compound 108

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine 9.7g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and H ₂ O 45ml and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 108 (10.6 g, yield 79%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 12] Synthesis of Compound 114

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2,4-di([1,1'-biphenyl]-4-yl)-6-(3-bromophenyl)-1,3,5-triazine 11.3 g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 1,4-dioxane 120ml and H ₂ O 45ml. Then, the mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 114 (12.3 g, yield 82%).

Mass : [(M+H) ⁺ ] : 715.66

[Synthesis Example 13] Synthesis of Compound 126

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-(3'-bromo-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine 9.7 g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 1,4-dioxane 120ml and H ₂ O 45ml. Then, the mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 126 (10.2 g, yield 76%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 14] Synthesis of Compound 133

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(4'-bromo-[1,1'-biphenyl]-3- yl)-6-phenyl-1,3,5-triazine 11.3g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) into 120ml of 1,4-dioxane and 45ml of H ₂ O, followed by heating under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 133 (11.5 g, yield 77%).

Mass : [(M+H) ⁺ ] : 715.66

[Synthesis Example 15] Synthesis of Compound 149

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-(3'-bromo-[1,1'-biphenyl]-4-yl)-4-(dibenzo[b,d]furan-4-yl )-6-phenyl-1,3,5-triazine 11.6g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq ) into 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 149 (12.1 g, yield 79%).

Mass : [(M+H) ⁺ ] : 729.65

[Synthesis Example 16] Synthesis of Compound 165

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2,4-di([1,1'-biphenyl]-3-yl)-6-(3-bromophenyl)-1,3,5-triazine 11.3 g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 1,4-dioxane 120ml and H ₂ O 45ml. Then, the mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 165 (12.3 g, yield 82%).

Mass : [(M+H) ⁺ ] : 715.66

[Synthesis Example 17] Synthesis of Compound 171

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-(3'-bromo-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine 9.7 g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 1,4-dioxane 120ml and H ₂ O 45ml. Then, the mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 171 (10 g, yield 75%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 18] Synthesis of Compound 176

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq) and 2-(3'-bromo-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine 9.7 g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 1,4-dioxane 120ml and H ₂ O 45ml. Then, the mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 176 (9.6 g, yield 72%).

Mass : [(M+H) ⁺ ] : 639.57

[Synthesis Example 19] Synthesis of Compound 189

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-(3''-bromo-[1,1':3',1''-terphenyl]-4-yl)-4,6-diphenyl- 1,3,5-triazine 11.3g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) 120 ml of dioxane and 45 ml of H ₂ O were put into it, and the mixture was stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 189 (10.9 g, yield 73%).

Mass : [(M+H) ⁺ ] : 715.66

[Synthesis Example 20] Synthesis of Compound 196

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-3-yl)-4-(3-bromophenyl)-6-(dibenzo[b,d]furan- 4-yl)-1,3,5-triazine 11.6g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) into 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 196 (11.5 g, yield 75%).

Mass : [(M+H) ⁺ ] : 729.65

[Synthesis Example 21] Synthesis of Compound 213

Compound A-5 synthesized in Preparation Example 5 {10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine 7.2g (20.9mmol, 1eq), Pd( PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq) and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O, followed by heating under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 213 (9.4 g, yield 80%).

Mass : [(M+H) ⁺ ] : 562.48

[Synthesis Example 22] Synthesis of Compound 228

Compound A-5 synthesized in Preparation Example 5 {10-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-4-yl)-6-(3-bromophenyl)-2-phenylpyrimidine 9.7g (20.9mmol, 1eq ), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O and heated under reflux for 5 hours. Stir. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 228 (9.8 g, yield 73%).

Mass : [(M+H) ⁺ ] : 638.58

[Synthesis Example 23] Synthesis of Compound 241

Compound A-4 synthesized in Preparation Example 4 {10-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-10H-dibenzo[b,e] [1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-(3'-bromo-[1,1'-biphenyl]-3-yl)-2,6-diphenylpyrimidine 9.7g (20.9mmol, 1eq) , Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), K ₂ CO ₃ 5.8g (151.8mmol, 4eq) was added to 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. . After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 241 (10.3 g, yield 77%).

Mass : [(M+H) ⁺ ] : 638.58

[Synthesis Example 24] Synthesis of Compound 266

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-(4'-bromo-[1,1'-biphenyl]-4-yl)-4,6-diphenylpyrimidine g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq) and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O and stirred under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 266 (9.5 g, yield 71%).

Mass : [(M+H) ⁺ ] : 638.58

[Synthesis Example 25] Synthesis of Compound 272

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-3-yl)-6-(3'-bromo-[1,1'-biphenyl]-4- yl) -2-phenylpyrimidine 11.3g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and 45ml of H ₂ O were added and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 272 (10.8 g, yield 72%).

Mass : [(M+H) ⁺ ] : 714.68

[Synthesis Example 26] Synthesis of Compound 283

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-(4'-bromo-[1,1'-biphenyl]-3- yl)-6-phenyl-1,3,5-triazine 11.3g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) into 120ml of 1,4-dioxane and 45ml of H ₂ O, followed by heating under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 283 (10.7 g, yield 71%).

Mass : [(M+H) ⁺ ] : 714.68

[Synthesis Example 27] Synthesis of Compound 291

Compound A-1 synthesized in Preparation Example 1 {10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-(4''-bromo-[1,1':3',1''-terphenyl]-3-yl)-2,6-diphenylpyrimidine g (20.9mmol, 1eq), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were added to 120ml of 1,4-dioxane and 45ml of H ₂ O. The mixture was heated under reflux and stirred for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 291 (10.8 g, yield 72%).

Mass : [(M+H) ⁺ ] : 714.68

[Synthesis Example 28] Synthesis of Compound 323

Compound A-2 synthesized in Preparation Example 2 {10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-4-yl)-2-(3'-bromo-[1,1'-biphenyl]-4- yl) -6-phenylpyrimidine 11.3g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and 45ml of H ₂ O were added and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 323 (10.9g, yield 73%).

Mass : [(M+H) ⁺ ] : 714.68

[Synthesis Example 29] Synthesis of Compound 372

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-3-yl)-2-(3'-bromo-[1,1'-biphenyl]-4- yl) -6-phenylpyrimidine 11.3g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and 45ml of H ₂ O were added and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 372 (9.9 g, yield 66%).

Mass : [(M+H) ⁺ ] : 714.68

[Synthesis Example 30] Synthesis of Compound 383

Compound A-3 synthesized in Preparation Example 3 {10-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-dibenzo[b,e][ 1,4]oxaborinine} 8g (20.9mmol, 1eq), 4-([1,1'-biphenyl]-4-yl)-6-(4'-bromo-[1,1'-biphenyl]-3- yl) -2-phenylpyrimidine 11.3g (20.9mmol, 1eq), Pd (PPh ₃ ) ₄ 1.0g (0.8mmol, 0.04eq), and K ₂ CO ₃ 5.8g (151.8mmol, 4eq) were mixed with 1,4-dioxane 120ml and 45ml of H ₂ O were added and heated under reflux for 5 hours. After completion of the reaction, after inactivation with a sufficient amount of water, the resulting solid was filtered to remove the solution, and then dried in an oven. The dried solid was purified by column chromatography to obtain compound 383 (10.3 g, yield 69%).

Mass : [(M+H) ⁺ ] : 714.68

[Example 1] - Fabrication of blue organic electroluminescent device

Compound 13 was purified by sublimation of high purity by a commonly known method, and then a green organic EL device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, methanol, etc., and drying, transfer to a UV OZONE cleaner (Power Sonic 405, Hwashin Tech), and then clean the substrate for 5 minutes using UV and transferred the substrate to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (Solus Advanced Materials Co., Ltd., 80 nm) / NPB (15 nm) / ADN + 5% DS-405 (Solus Advanced Materials Co., Ltd., 30 nm) / compound 13 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to fabricate an organic electroluminescent device. The structures of NPB and ADN used at this time are as follows.

[Examples 2 to 30] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that each of the electron transport layer materials in Table 1 was used instead of Compound 13 used as the electron transport layer material.

[Comparative Example 1] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that Alq ₃ was used instead of Compound 13 used as the electron transport layer material. The structure of Alq ₃ used at this time is as follows.

[Comparative Example 2] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-1 was used instead of Compound 13 used as the electron transport layer material.

[Comparative Example 3] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except for using the following compound S-2 instead of compound 13 used as the electron transport layer material.

[Comparative Example 4] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-3 was used instead of Compound 13 used as the electron transport layer material.

[Comparative Example 5] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-4 was used instead of Compound 13 used as the electron transport layer material.

[Comparative Example 6] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except for using the following compound S-5 instead of compound 13 used as the electron transport layer material.

[Comparative Example 7] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except for using the following compound S-6 instead of compound 13 used as the electron transport layer material.

[Evaluation Example 1]

For the blue organic EL devices prepared in Examples 1 to 30 and Comparative Examples 1 to 5, driving voltage, emission peak and current efficiency were measured at a current density of 10 mA/cm 2 , and the results are shown in Table 1 below. showed up

Sample electron transport layer material Driving voltage (V) Emission peak (nm) Current efficiency (cd/A) Example 1 compound 13 3.3 454 8.0 Example 2 compound 23 3.1 454 8.2 Example 3 compound 26 3.4 453 7.9 Example 4 compound 33 3.3 452 7.8 Example 5 compound 39 3.3 453 8.0 Example 6 compound 46 3.2 454 8.0 Example 7 compound 57 3.4 455 7.9 Example 8 compound 63 3.3 455 8.2 Example 9 compound 72 3.3 452 8.1 Example 10 compound 96 3.4 453 7.8 Example 11 compound 108 3.3 454 7.9 Example 12 compound 114 3.3 452 8.0 Example 13 compound 126 3.3 453 7.9 Example 14 compound 133 3.2 454 8.0 Example 15 compound 149 3.3 454 8.2 Example 16 compound 165 3.3 452 8.1 Example 17 compound 171 3.4 454 8.0 Example 18 compound 176 3.5 453 7.6 Example 19 compound 189 3.2 454 7.9 Example 20 compound 196 3.1 453 8.1 Example 21 compound 213 3.1 451 8.1 Example 22 compound 228 3.2 451 8.1 Example 23 compound 241 3.1 452 8.1 Example 24 compound 266 3.0 451 8.1 Example 25 compound 272 3.2 450 8.1 Example 26 compound 283 3.1 453 8.1 Example 27 compound 291 3.2 452 8.1 Example 28 compound 323 3.3 451 8.1 Example 29 compound 372 3.2 451 8.1 Example 30 compound 383 3.1 452 8.1 Comparative Example 1 Alq ₃ 4.6 457 5.6 Comparative Example 2 Compound S-1 3.7 459 6.9 Comparative Example 3 Compound S-2 3.9 455 6.6 Comparative Example 4 Compound S-3 4.4 455 7.3 Comparative Example 5 Compound S-4 4.3 455 7.4 Comparative Example 6 Compound S-5 5.2 451 4.5 Comparative Example 7 Compound S-6 5.5 454 3.9

As shown in Table 1, the blue organic electroluminescent devices of Examples 1 to 30 using the compound of the present invention as an electron transport layer material are conventional blue organic electroluminescent devices of Comparative Example 1 using Alq ₃ as an electron transport layer material. It was found that it exhibited significantly better performance in terms of driving voltage, emission peak, and current efficiency compared to .

In addition, the blue organic electroluminescent devices of Examples 1 to 30 include compounds S-1 to S-4 that do not contain a dibenzo[b,e][1,4]oxaborinin moiety as electron transport layer materials. Compared to the blue organic electroluminescent devices of Comparative Examples 2 to 5, it was confirmed that they had a low driving voltage and high current efficiency.

In addition, the blue organic light emitting devices of Comparative Examples 6 to 7 each included compounds S-5 and S-6 as electron transport layer materials. Since these compounds S-5 and S-6 are substituted with an arylene (eg fluorene group) and a carbazole group, respectively, as an electron donor to the dibenzo[b,e][1,4]oxaborinin moiety, dibenzo[ The b,e][1,4]oxaborinin moiety acts as a relatively strong electron attractor, which positions the distribution of LUMO. However, the compounds S-5 and S-6 have lower electron transport ability than the compounds of the present invention including azine. For this reason, it can be estimated that the blue organic light emitting devices of Comparative Examples 6 to 7 have a high driving voltage and low luminous efficiency due to the collapse of the charge balance of the entire device compared to the organic light emitting devices of Examples 1 to 30.

[Example 31] Fabrication of blue organic electroluminescent device

After subjecting Compound 13 to high-purity sublimation purification by a conventionally known method, a blue organic electroluminescent device was manufactured according to the following procedure.

A glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After the distilled water cleaning is finished, ultrasonic cleaning is performed with solvents such as isopropyl alcohol, acetone, and methanol, and after drying, transfer to a UV OZONE cleaner (Power Sonic 405, Hwashin Tech), and then clean the substrate for 5 minutes using UV and transferred the substrate to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (80 nm) / NPB (15 nm) / ADN + 5% DS-405 (Solus Advanced Materials Co., Ltd., 30 nm) / Compound 13 (5 nm) / Alq ₃ ( 25 nm) / LiF (1 nm) / Al (200 nm) in this order to prepare an organic electroluminescent device. The structures of NPB, ADN and Alq ₃ used at this time are as follows.

[Examples 32 to 60] - Fabrication of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that each of the electron transport auxiliary layer materials in Table 2 was used instead of Compound 13 used as the electron transport auxiliary layer material.

[Comparative Example 8] - Preparation of blue organic electroluminescent device

Fabrication of a blue organic electroluminescent device in the same manner as in Example 31, except that the electron transport layer material Alq ₃ was deposited at 30 nm instead of 25 nm without using Compound 13 used as the electron transport auxiliary layer material. did

[Comparative Example 9] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-1 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-1 used at this time is the same as that described in Comparative Example 2, so it is omitted.

[Comparative Example 10] - Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-2 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-2 used at this time is the same as that described in Comparative Example 3, so it is omitted.

[Comparative Example 11] - Fabrication of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-3 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-3 used at this time is the same as that described in Comparative Example 4, so it is omitted.

[Comparative Example 12] - Fabrication of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-4 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-4 used at this time is the same as that described in Comparative Example 5, so it is omitted.

[Comparative Example 13] - Fabrication of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-5 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-5 used at this time is the same as that described in Comparative Example 6, so it is omitted.

[Comparative Example 14] - Fabrication of blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except that Compound S-6 was used instead of Compound 1 used as the electron transport auxiliary layer material. The structure of the compound S-6 used at this time is the same as that described in Comparative Example 7, so it is omitted.

[Evaluation example 2]

For the blue organic EL devices prepared in Examples 31 to 60 and Comparative Examples 6 to 10, driving voltage, emission peak and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 2 below. showed up

Sample Electron Transport Auxiliary Layer Materials Driving voltage (V) Emission peak (nm) Current efficiency (cd/A) Example 31 compound 13 3.2 454 7.9 Example 32 compound 23 3.1 454 8.3 Example 33 compound 26 3.3 453 7.8 Example 34 compound 33 3.2 452 7.9 Example 35 compound 39 3.3 453 7.8 Example 36 compound 46 3.2 454 8.1 Example 37 compound 57 3.4 455 7.7 Example 38 compound 63 3.3 455 8.0 Example 39 compound 72 3.2 452 8.1 Example 40 compound 96 3.3 453 7.7 Example 41 compound 108 3.2 454 8.1 Example 42 compound 114 3.4 452 7.8 Example 43 compound 126 3.3 453 7.9 Example 44 compound 133 3.2 454 8.1 Example 45 compound 149 3.1 454 8.3 Example 46 compound 165 3.4 452 7.8 Example 47 compound 171 3.3 454 8.0 Example 48 compound 176 3.5 453 7.7 Example 49 compound 189 3.2 454 8.0 Example 50 compound 196 3.2 453 8.2 Example 51 compound 213 3.2 451 8.3 Example 52 compound 228 3.1 451 8.2 Example 53 compound 241 3.2 452 8.2 Example 54 compound 266 3.1 451 8.1 Example 55 compound 272 3.1 450 8.0 Example 56 compound 283 3.0 453 8.3 Example 57 compound 291 3.2 452 8.3 Example 58 compound 323 3.2 451 8.0 Example 59 compound 372 3.3 451 7.9 Example 60 compound 383 3.1 452 8.2 Comparative Example 8 _- 4.7 457 5.8 Comparative Example 9 Compound S-1 3.8 459 6.8 Comparative Example 10 Compound S-2 4.1 455 6.6 Comparative Example 11 Compound S-3 4.3 455 7.1 Comparative Example 12 Compound S-4 4.4 455 7.2 Comparative Example 13 Compound S-5 5.4 451 4.5 Comparative Example 14 Compound S-6 5.5 454 4.0

As shown in Table 2, the blue organic electroluminescence devices of Examples 31 to 60 using the compound of the present invention as the electron transport auxiliary layer material are the blue organic electroluminescent devices of Comparative Example 8 that do not use the electron transport auxiliary layer material. It was found that the device exhibited significantly better performance in terms of driving voltage, emission peak, and current efficiency compared to the device.

In addition, the blue organic electroluminescent devices of Examples 31 to 60 use compounds S-1 to S-4 that do not contain a dibenzo[b,e][1,4]oxaborinin moiety as an electron transport auxiliary layer material. Compared to the blue organic electroluminescent devices of Comparative Examples 9 to 12 and the blue organic electroluminescent devices of Comparative Examples 13 to 14 containing compounds S-5 and S-6 not containing an azine group as electron transport auxiliary layer materials. It was confirmed that the driving voltage and current efficiency were excellent.

100: anode, 200: cathode,
300: organic material layer, 310: hole injection layer,
320: hole transport layer, 330: light emitting layer,
340: electron transport layer, 350: electron injection layer,
360: electron transport auxiliary layer

Claims (11)

A compound represented by Formula 1 or 2:
[Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2,
n1 and n2 are each an integer from 0 to 4;
L ₁ and L ₂ are each independently a single bond or selected from the group consisting of a C ₆ ~ C ₂₄ arylene group and a heteroarylene group having 3 to 24 nuclear atoms;
Sub ₁ and Sub ₂ are each a substituent represented by Formula 3 below,
[Formula 3]

In Formula 3,
Z ₁ to Z ₃ are the same as or different from each other, and are each independently N or C(R ₆ ), provided that at least one of Z ₁ to Z ₃ is N, wherein, when C(R ₆ ) is plural, a plurality of R ₆ are the same as or different from each other;
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently hydrogen, deuterium, tritium, C ₂ ~C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, nucleus Heterocycloalkyl group having 3 to 40 atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~C ₆₀ aryloxy group, C ₁ ~C ₄₀ alkylsilyl group, C ₆ ~C ₆₀ arylsilyl group, C ₁ ~C ₄₀ alkylboron group, C ₆ ~C ₆₀ arylboron group, C ₆ It is selected from the group consisting of ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ arylamine group,
a is an integer from 0 to 3;
b is an integer from 0 to 4;
c is an integer from 0 to 5;
d is an integer from 0 to 4;
e is an integer from 0 to 4;
R ₁ to R ₆ are the same as or different from each other, and are each independently hydrogen, deuterium, tritium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₁ ~C ₄₀ alkyl group, C ₆ ~C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ selected from the group consisting of arylamine group, or condensation by combining with adjacent groups form a ring,
Arylene and heteroarylene groups of L ₁ and L ₂ , Ar ₁ and Ar ₂ of alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, alkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, An alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group, and an arylamine group, an alkenyl group of R ₁ to R ₆ , an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, An alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group, an arylamine group, and a condensed ring Each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C It is substituted or unsubstituted with one or more substituents selected from the group consisting of a ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group, and when the substituents are plural, they are the same as or different from each other). According to claim 1,
The compound represented by Formula 1 or 2 is a compound represented by Formula 4 or 5:
[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,
n1, n2, Sub ₁ , Sub ₂ , a, b, c, d, e, R ₁ to R ₅ are each as defined in claim 1,
f is an integer from 0 to 4;
R ₇ is deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C It is selected from the group consisting of a ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group). According to claim 2,
remind

and

Each is a direct bond or selected from the group consisting of the following linker groups L-1 to L-14:

(In the linker groups L-1 to L-14,
f and R ₇ are each as defined in claim 2). According to claim 1,
The substituent represented by Formula 3 is a substituent selected from the group consisting of the following substituents S1-1 to S1-3, a compound:

(In the above substituents S1-1 to S1-3,
Ar ₁ , Ar ₂ , and R ₆ are each as defined in claim 1). According to claim 1,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently selected from the group consisting of a C ₆ ~ C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms;
The aryl group and heteroaryl group of Ar ₁ and Ar ₂ are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy Group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ arylphosphine oxide group and C ₆ ~ C ₆₀ substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine group, the substituent When are plural, they are the same or different from each other). According to claim 1,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently a substituent selected from the group consisting of the following substituents S2-1 to S2-12, compound:

(In the above substituents S2-1 to S2-12,
R ₈ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl It is selected from the group consisting of a boron group, a C ₆ ~ C ₆₀ arylphosphine group, a C ₆ ~ C ₆₀ arylphosphine oxide group, and a C ₆ ~ C ₆₀ arylamine group). According to claim 1,
The compound represented by Formula 1 or 2 is a compound represented by any one of Formulas 6 to 11:
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

(In Chemical Formulas 6 to 11,
n1, n2, a, b, c, d, e, R ₁ to R ₅ , Ar ₁ and Ar ₂ are each as defined in claim 1,
f is an integer from 0 to 4;
R ₇ is deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C It is selected from the group consisting of a ₆ ~ C ₆₀ arylphosphine oxide group and a C ₆ ~ C ₆₀ arylamine group). According to claim 7,
In Formulas 6 to 8, at least one of R ₁ to R ₃ , R ₇ , Ar ₁ and Ar ₂ is deuterium (D),
In Formulas 9 to 11, at least one of R ₄ to R ₅ , R ₇ , Ar ₁ and Ar ₂ is deuterium (D), a compound. According to claim 1,
The compound represented by Formula 1 or 2 is any one of the following compounds 1 to 400:

. anode; cathode; Including one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers includes an organic electroluminescent device comprising the compound according to any one of claims 1 to 9. According to claim 10,
The organic material layer containing the compound is at least one selected from the group consisting of a light emitting layer, an electron transport layer and an electron transport auxiliary layer, an organic electroluminescent device.

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