KR20210156587A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound having excellent light emitting ability and an organic electroluminescent device comprising the same, and the compound according to the present invention is used in an organic matter layer material of the organic electroluminescent device, preferably an electron transport layer material and an electron transport auxiliary layer material, so that it is possible to improve the luminous efficiency, driving voltage, lifespan, etc. of the organic electroluminescent device.

Description

Organic light emitting compound and organic electroluminescent device using same

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

A study on organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices') that led to blue electroluminescence using anthracene single crystals in 1965, starting with Bernanose's observation of organic thin film emission in the 1950s, began in 1987. (Tang) presented an organic EL device having a stacked structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high-efficiency, long-life organic EL device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of a specialized material used for this.

When a voltage is applied between the two electrodes of the organic electroluminescent 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, an exciton is formed, and when the exciton falls to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

The material 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 emission color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better natural colors. In addition, in order to increase color purity and increase luminous 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 four times compared to fluorescence, and thus, attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Until now, hole injection layer, hole transport layer. As the hole blocking layer and the electron transporting layer, NPB, BCP, Alq _3, etc. represented by the following chemical formulas are widely known, and anthracene derivatives have been reported as fluorescent dopant/host materials as light emitting materials. In particular, among the light emitting materials, as a phosphorescent material having a great advantage in terms of efficiency improvement _{, a metal complex compound containing Ir such as Firpic, Ir(ppy) 3} , (acac)Ir(btp) _{2 ,} etc. is a blue, green, and red dopant material. is being used as So far, CBP has shown excellent properties as a phosphorescent host material.

However, although the existing materials have advantages in terms of luminescent properties, they are not satisfactory in terms of lifespan in organic EL devices due to their low glass transition temperature and very poor thermal stability.

Republic of Korea Patent Publication No. 10-2015-0033082 (published date: 04. 01, 2015)

In the present invention, a specific heterocyclic compound can be applied to an organic electroluminescent device, and the specific heterocyclic compound is used as an electron transport layer (ETL) material, which is a common layer of an organic electroluminescent device. An object of the present invention is to provide a novel organic compound.

In addition, the present invention includes a material for an electron transport layer with improved lifespan and improved electron injection and transport ability, a hole transport layer material with improved hole injection and transport ability, and a material for the hole transport layer including the novel organic compound, which exhibits low driving voltage and high luminous efficiency, and includes the same Another object of the present invention is to provide an organic electroluminescent device.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms,

n is an integer from 0 to 3,

A and B are each independently a substituent represented by any one of the following Chemical Formulas 2 to 4,

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4,

* is the part where the bond is made,

A plurality of Xs are the same or different from each other, and each independently C (R) or N, but X represented by Formula 2 and Formula 3 represented by A is at least two or more N,

R is hydrogen, deuterium, halogen, cyano group, nitro group, C1~ C40 alkyl group, C2~ C4 ₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, 3 nuclear atoms To 40 heterocycloalkyl 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 ₃ ~ 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 ₆ ~ mono or diaryl phosphine of C ₆₀ blood group and a C ₆ ~ C is selected from the ₆₀ group consisting of aryl amines, form a condensed ring of the group aliphatic, aromatic, aliphatic hetero, or aromatic heterocyclic group which are adjacent to each other, or to achieve a spiro bond there is,

R of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, an aryl group Phosphine group, mono or diarylphosphinyl group and arylsilyl group are 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 ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl Amine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C substituted with at least ₆₀ of the aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ selected from the group consisting arylsilyl of C ₆₀ one kind of substituent or being unsubstituted , when substituted with a plurality of substituents, they may be the same or different from each other,

m is an integer from 1 to 3,

When Ar1 is plural, the same or different from each other, and each independently is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, It is a substituted or unsubstituted heteroaryl group, and may form a condensed ring with adjacent X,

Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

In addition, the present invention includes an anode, a cathode, and one or more organic material layers interposed between the positive and negative electrodes, wherein at least one of the one or more organic layers includes a compound represented by Formula 1 above. A light emitting device is provided.

Here, at least one of the one or more organic material layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, It is preferably a transport layer, an electron transport auxiliary layer and/or a light emitting layer. In this case, the compound represented by Formula 1 is an electron transport layer material, an electron transport auxiliary layer material, and/or a light emitting layer material.

Since the compound of the present invention has excellent luminous efficiency, driving voltage, lifespan, etc., it can be usefully applied as an organic material layer material of an organic electroluminescent device. , life, efficiency, etc. are greatly improved, so that it can be effectively applied to a full-color display panel.

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

Hereinafter, the present invention will be described in detail.

1. Organic compounds

The present invention provides a novel fluorene-based compound excellent in luminous efficiency, driving voltage, lifespan, and the like.

Specifically, in the novel organic compound according to the present invention, an aliphatic ring group, such as a cyclohexyl group, substituted in a spiro form at the 9th position of fluorene is adopted as a core, and a phenyl group of the core structure is adopted. An electron withdrawing group (EWG) with excellent electron transport ability is combined to form a basic skeleton.

The compound represented by Formula 1 having such a structure is electrochemically stable compared to the conventionally known dimethyl fluorene structure as an aliphatic ring group is formed at the 9th position of fluorene. In addition, physicochemical properties more suitable for electron injection and electron transport by introducing an electron withdrawing group, a functional group with strong electron withdrawing capability (EWG), in a double cross type on both sides of the core to improve the electron transfer speed be able to have

The cross shape of the dual electron withdrawing groups (Dual EWG) may be introduced as a three-dimensional structure in the form of a vertical orientation and a horizontal orientation. The compound represented by Formula 1 of the present invention has a twisted and rigid structure due to the vertical alignment, and has the following advantages. It is possible to prevent excitons generated in the light emitting layer derived from high triplet energy from diffusing (moving) into an adjacent electron transport layer or hole transport layer. Accordingly, the number of excitons contributing to light emission in the light emitting layer may be increased to improve luminous efficiency of the device, and durability and stability of the device may be improved to effectively increase the lifetime of the device. In addition, it is excellent in terms of high glass transition temperature (Tg) and thermal stability, and induces a deep HOMO level (Deep HOMO) as an electron-rich point occurs.

Additionally, the compound represented by Formula 1 of the present invention has a dipole orientation structure due to the horizontal orientation, so that fast electron mobility is improved as well as a deep LUMO level (Deep LUMO). ) to induce high electron mobility (High electron mobility) has an advantage. Most of the materials developed due to the above effects exhibit low voltage driving, which results in improved lifespan.

Therefore, the novel organic compound according to the present invention maintains a planar shape using fluorene substituted with cyclohexyl, which is advantageous for fast electron transfer speed, high efficiency, high lifespan, and low driving voltage, and can have a thermally stable structure, It has the advantage of having a high triple window energy and separation of HOMO and LUMO due to a cross-shaped three-dimensional structure.

In addition, in the present invention, a dibenzo-based moiety [eg, dibenzofuran (DBF) or dibenzothiophene (DBT)]. It can be applied as a green phosphorescent material with excellent luminous efficiency through the combination of such a dibenzo-based moiety and a nitrogen-containing aromatic ring (eg, pyridine, pyrazine, triazine), which is a strong electron-withdrawing group (EWG). In addition, it is possible to drive at a low voltage, thereby exhibiting an effect of increasing the lifespan, and has excellent device characteristics due to thermal stability, high glass transition temperature characteristics, and uniform morphology.

As described above, the compound represented by Formula 1 of the present invention is an organic material layer material of an organic electroluminescent device, preferably a light emitting layer material (blue, green and/or red phosphorescent host material), electron transport layer/injection layer material, hole When applied as a transport layer/injection layer material, a light emitting auxiliary layer material, or a life improvement layer material, the performance and lifespan characteristics of the organic electroluminescent device can be greatly improved. As a result, such an organic electroluminescent device can maximize the performance of a full color organic light emitting panel.

In the compound represented by Formula 1, L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms, n is an integer of 0 to 3 to be.

In Formulas 2 to 4, * is a portion where a bond is formed, a plurality of Xs are the same or different from each other, and each independently C(R) or N, but X represented by Formulas 2 and 3 represented by A is At least two or more are N, wherein R is hydrogen, deuterium, halogen, cyano group, nitro group, C1~ C40 alkyl group, C2~ C4 ₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ of a cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ of Aryloxy group, C ₃ ~ 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 of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diaryl phosphinyl group, and a C ₆ ~ C ₆₀ arylamine group, and a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero group with adjacent groups may form or form a spiro bond.

R of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, an aryl group Phosphine group, mono or diarylphosphinyl group and arylsilyl group are 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 ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl Amine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C substituted with at least ₆₀ of the aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ selected from the group consisting arylsilyl of C ₆₀ one kind of substituent or being unsubstituted , when substituted with a plurality of substituents, they may be the same or different from each other, m is an integer from 1 to 3, and when Ar1 is plural, the same or different from each other, and each independently substituted or unsubstituted alkyl Or, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and may form a condensed ring with the adjacent X.

Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

Specifically, the compound represented by Formula 2 may be represented by any one of Formulas 5 to 10 below.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 5 to 10, * is a portion to which a bond is formed, Y is hydrogen, deuterium, halogen, cyano group, nitro group, C1-C40 alkyl group, C2-C4 ₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, 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 ₃ ~ 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 aryl phosphine is selected from the pingi, C ₆ ~ C ₆₀ mono or diaryl phosphine group P and the group consisting of C ₆ ~ C ₆₀ aryl group of an amine of,

X and Ar1 are each as defined in Formula 1

In addition, the compound represented by Formula 3 may be represented by Formula 11 below.

[Formula 11]

In Formula 11, * is a moiety to which a bond is formed, and X is as defined in Formula 1.

Specifically, Formula 5 may be embodied as any one of Formula 14 or Formula 15 below.

[Formula 14]

[Formula 15]

In Formula 14 or Formula 15, * is a portion where a bond is formed, and Ar1 is as defined in Formula 1.

Specifically, Formula 6 may be embodied as Formula 16 below.

[Formula 16]

In Formula 16, * is a moiety to which a bond is formed, and Ar1 is as defined in Formula 1.

Specifically, Formula 4 may be embodied as Formula 17 below.

[Formula 17]

In Formula 17, * is a moiety to which a bond is formed.

The L may be a single bond or a linker selected from the following L-1 to L-3.

In L-1 to L-3, * is a portion where a bond is formed.

The compound represented by Formula 1 according to an example of the present invention described above may be further specified as a compound represented by any one selected from the group consisting of the compounds exemplified below. However, the compound represented by Formula 1 of the present invention is not limited by those exemplified below.

In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched 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 linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

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

In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form 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" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are 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 further, 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, and carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

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

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means an alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. may include Examples of 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, "arylamine" refers to an amine substituted with an aryl having 6 to 40 carbon atoms.

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 at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" refers to silyl substituted with aryl having 5 to 40 carbon atoms.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

2. Electron transport layer

In the compound represented by Formula 1 according to the present invention, an aliphatic ring group, for example, a cyclohexyl group substituted in a spiro form at the 9th position of fluorene is adopted as a core, and a phenyl group of the core structure is adopted. Since the electron withdrawing group (EWG) having excellent electron transport ability is combined with the electron-withdrawing group (EWG) to have strong electron-receiving properties, when the compound of Formula 1 is applied as an electron transport layer, it can well accept electrons from the cathode, so it is used as a light emitting layer Electrons can be transferred smoothly. Therefore, the present invention can be used as the compound for the electron transport layer represented by the formula (1).

The electron transport layer (ETL) serves to receive electrons from the cathode and move the electrons to the light emitting layer. Accordingly, the stronger the material used for the electron transport layer, the more suitable it is to move electrons.

Specifically, the electron transport layer (ETL) serves to move electrons injected from the cathode to an adjacent layer, specifically, a light emitting layer, and the compound represented by Formula 1 may be used alone as an electron transport layer (ETL) material. , or may be mixed with an electron transport layer material known in the art.

The electron transport layer material that can be mixed with the compound of Formula 1 includes an electron transport material commonly known in the art, and non-limiting examples of the electron transport material that can be used include an oxazole-based compound, an isoxazole-based compound, and a tria. Sol-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene-based compounds, aluminum complexes (eg, Alq3 (tris(8-quinolinolato) -aluminum (tris(8-quinolinolato)-aluminium) BAlq, SAlq, Almq3, gallium complex (eg Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)), etc. These may be used alone or in two types more can be mixed.

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

3. Organic electroluminescent device

Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) including the compound represented by Formula 1 according to the present invention.

Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is and a compound represented by Formula 1 above. In this case, the compound may be used alone or in mixture of two or more.

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a light emission auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, and at least one organic material layer is represented by Formula 1 including compounds. Specifically, it is preferable that the organic material layer including the compound of Formula 1 is a light emitting layer, an electron transport layer, and an electron transport auxiliary layer.

The light emitting layer of the organic electroluminescent device according to the present invention includes a host material and a dopant material, and in this case, the compound of Formula 1 may be included as the host material. In addition, the light emitting layer of the present invention may include a known compound in the art other than the compound of Formula 1 as a host.

When the compound represented by Formula 1 is included as a light emitting layer material of an organic electroluminescent device, preferably a blue, green, or red phosphorescent host material, since the bonding force between holes and electrons in the light emitting layer is increased, the efficiency of the organic electroluminescent device (luminous efficiency and power efficiency), lifespan, luminance, and driving voltage can be improved. Specifically, the compound represented by Formula 1 is preferably included in the organic electroluminescent device as a green and/or red phosphorescent host, a fluorescent host, or a dopant material. In particular, the compound represented by Formula 1 of the present invention is preferably a green phosphorescent exciplex N-type host material of the light emitting layer having high efficiency.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and a cathode are sequentially stacked. At this time, at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1, preferably the light emitting layer, more preferably a phosphorescent host may include a compound represented by Formula 1 above. Meanwhile, an electron injection layer may be additionally stacked on the electron transport layer.

The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.

The organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. have.

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

The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, and for example, a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, and a sheet may be used.

In addition, as the cathode material, a cathode material known in the art may be used without limitation. For example, metals such as vanadium, chromium, copper, zinc, 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 SnO2: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, as the negative electrode material, any negative electrode material known in the art may be used without limitation. For example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; and a multilayer structure material such as LiF/Al or LiO2/Al, but is not limited thereto.

In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and conventional materials known in the art may be used without limitation.

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

[Preparation Example 1] Synthesis of 7'-chloro-3'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene]

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 2 -bromo-9,9-dimethyl-9H-fluorene (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were mixed with 1000 ml of Toluene, Ethanol 250ml, _{put into 250ml of H 2} O, heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 7'-chloro-3'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene was used by column chromatography. ] (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.74(d, 1H), 7.68(d, 1H), 7.39(d, 1H), 7.84(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55 (d, 1H), 7.28 (t, 1H), 7.38 (t, 1H), 7.90 (d, 1H), 8.09 (d, 1H), 7.78 (d, 1H)

[LCMS]: 461

In the same way as above, instead of 2-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-dimethyl-9H-fluorene or 2'-bromospiro [cyclohexane-1,9'-fluorene] or By using 4'-bromospiro [cyclohexane-1,9'-fluorene], the following target compound can be synthesized.

[Preparation Example 2] Synthesis of 6'-chloro-3'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene]

2-(3'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 2 -bromo-9,9-dimethyl-9H-fluorene (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were mixed with 1000 ml of Toluene, Ethanol 250ml, _{put into 250ml of H 2} O, heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 6'-chloro-3'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene was used by column chromatography. ] (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.76(d, 1H), 7.68(d, 1H), 7.39(d, 1H), 7.84(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55 (d, 1H), 7.28 (t, 1H), 7.38 (t, 1H), 7.90 (d, 1H), 8.09 (d, 1H), 7.78 (d, 1H)

[LCMS]: 461

In the same way as above, instead of 2-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-dimethyl-9H-fluorene or 2'-bromospiro [cyclohexane-1,9'-fluorene] or By using 4'-bromospiro [cyclohexane-1,9'-fluorene], the following target compound can be synthesized.

[Preparation Example 3] Synthesis of 7'-chloro-2'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene]

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 2 -bromo-9,9-dimethyl-9H-fluorene (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were mixed with 1000 ml of Toluene, Ethanol 250ml, _{put into 250ml of H 2} O, heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 7'-chloro-2'-(9,9-dimethyl-9H-fluoren-2-yl)spiro[cyclohexane-1,9'-fluorene was used by column chromatography. ] (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.75(d, 1H), 7.68(d, 1H), 7.39(d, 1H), 7.84(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55 (d, 1H), 7.28 (t, 1H), 7.48 (t, 1H), 7.90 (d, 1H), 8.09 (d, 1H), 7.78 (d, 1H)

[LCMS]: 461

In the same way as above, instead of 2-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-dimethyl-9H-fluorene or 2'-bromospiro [cyclohexane-1,9'-fluorene] or By using 4'-bromospiro [cyclohexane-1,9'-fluorene], the following target compound can be synthesized.

[Preparation Example 4] Synthesis of 7-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 7 -bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) 1000ml of Toluene, 250ml of Ethanol, 250ml of H ₂ O It was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 7-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-9,9-dimethyl-9H-fluorene was used by column chromatography. -2-carbonitrile (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.75(d, 1H), 7.68(d, 1H), 7.39(d, 1H), 7.84(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55(s, 1H), 7.48(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H)

[LCMS]: 486

In the same manner as above, 5-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile or 2'-bromospiro[cyclohexane-] instead of 7-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile Using 1,9'-fluorene]-7'-carbonitrile or 5'-bromospiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, the following target compound can be synthesized.

[Preparation Example 5] Synthesis of 7-(3'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile

2-(3'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 7 -bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) 1000ml of Toluene, 250ml of Ethanol, 250ml of H ₂ O It was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 7-(3'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-9,9-dimethyl-9H-fluorene was used by column chromatography. -2-carbonitrile (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.73(d, 1H), 7.68(d, 1H), 7.39(d, 1H), 7.84(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55(s, 1H), 7.48(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H)

[LCMS]: 486

In the same manner as above, 5-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile or 2'-bromospiro[cyclohexane-] instead of 7-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile Using 1,9'-fluorene]-7'-carbonitrile or 5'-bromospiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, the following target compound can be synthesized.

[Preparation Example 6] Synthesis of 7-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 7 -bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile (34.6 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) 1000ml of Toluene, 250ml of Ethanol, 250ml of H ₂ O It was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 7-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-9,9-dimethyl-9H-fluorene was used by column chromatography. -2-carbonitrile (42.05 g, yield 72%) was obtained.

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.73(d, 1H), 7.68(d, 1H), 7.41(d, 1H), 7.86(d, 1H), 8.18(s, 1H), 7.89(s, 1H), 1.60(m) , 2H), 7.55(s, 1H), 7.48(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H)

[LCMS]: 486

In the same manner as above, 5-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile or 2'-bromospiro[cyclohexane-] instead of 7-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile Using 1,9'-fluorene]-7'-carbonitrile or 5'-bromospiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, the following target compound can be synthesized.

[Preparation Example 7] Synthesis of 4-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)benzonitrile

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 4 -bromobenzonitrile (23.06 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were added to 1000 ml of Toluene, 250 ml of Ethanol, 250 ml of H ₂ O, and 12 hours It was heated and refluxed for a while. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound, 4-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)benzonitrile (33.73 g, yield 72%), was obtained by column chromatography. got it

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.73(d, 1H), 7.68(d, 1H), 7.40(s, 1H), 7.84(d, 1H), 7.86(d, 1H), 7.89(d, 1H), 7.90(d) , 1H), 7.65 (d, 1H), 7.67 (d, 1H)

[LCMS]: 369

In the same way as above, 2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- (2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3'-chlorospiro[cyclohexane -1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane can be used to synthesize the target compound as follows.

[Preparation Example 8] Synthesis of 8-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 8 -bromo-4a,5-dihydroquinoline (26.61 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were mixed with 1000 ml of Toluene, 250 ml of Ethanol, and H ₂ O 250ml and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 8-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline (33.73 g, yield 72%) was obtained by column chromatography. got it

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.73(d, 1H), 7.68(d, 1H), 7.40(s, 1H), 7.84(d, 1H), 7.86(d, 1H), 7.89(d, 1H), 7.90(d) , 1H), 7.65 (d, 1H), 7.67 (d, 1H), 7.66 (t, 1H), 7.69 (t, 1H)

[LCMS]: 395

In the same way as above, 2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- (2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3'-chlorospiro[cyclohexane -1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane can be used to synthesize the following target compound.

[Preparation Example 9] Synthesis of 5-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline

2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.0 g, 126.66 mmol), 5 -bromoquinoline (26.61 g, 126.66 mmol) and Pd(PPh ₃ ) ₄ (7.32 g, 6.33 mmol), K ₂ CO ₃ (35.01 g, 253.32 mmol) were added to 1000 ml of Toluene, 250 ml of Ethanol, 250 ml of H ₂ O, and 12 hours It was heated and refluxed for a while. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound, 5-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline (33.73 g, yield 72%), was obtained by column chromatography. got it

¹ H-NMR: δ 1.44 (t, 1H), 1.46 (t, 1H), 1.43 (t, 2H), 1.53 (t, 2H), 1.90 (t, 2H), 2.15 (t, 2H), 7.56 ( s, 1H), 7.73(d, 1H), 7.68(d, 1H), 7.39(s, 1H), 7.84(d, 1H), 7.86(d, 1H), 7.89(d, 1H), 7.90(d) , 1H), 7.65 (d, 1H), 7.64 (d, 1H), 7.62 (t, 1H), 7.69 (t, 1H)

[LCMS]: 395

In the same way as above, 2-(2'-chlorospiro[cyclohexane-1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- (2'-chlorospiro[cyclohexane-1,9'-fluoren]-7'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3'-chlorospiro[cyclohexane -1,9'-fluoren]-6'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane can be used to synthesize the target compound as follows.

* Synthesis example

[Synthesis Example 1] Synthesis of compound A-1

The compound of the preparation example is the target compound (10g, 18.10mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.84 g, 18.10 mmol) and Pd(PPh ₃ ) ₄ (1.05 g, 0.9 mmol), K ₂ CO ₃ (5 g, 36.19 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-1 (8.57 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-1, C-1, D-1, E-1, F-1, G-1, respectively , H-1 can be synthesized.

[Synthesis Example 2] Synthesis of compound A-2

The compound of the preparation example is the target compound (10g, 18.10mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.84 g, 18.10 mmol) and Pd(PPh ₃ ) ₄ (1.05 g, 0.9 mmol), K ₂ CO ₃ (5 g, 36.19 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-2 (8.57 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-2, C-2, D-2, E-2, F-2, G-2, respectively , H-2 can be synthesized.

[Synthesis Example 3] Synthesis of compound A-3

The compound of the preparation example is the target compound (10g, 16.87mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.52 g, 16.87 mmol) and Pd(PPh ₃ ) ₄ (0.97 g, 0.84 mmol), K ₂ CO ₃ (4.66 g, 33.75 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-3 (8.48 g, yield 72%) was obtained by column chromatography.

[LCMS]: 697

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-3, C-3, D-3, E-3, F-3, G-3, respectively , H-3 can be synthesized.

[Synthesis Example 4] Synthesis of compound A-4

The compound of the preparation example is the target compound (10g, 16.87mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.52 g, 16.87 mmol) and Pd(PPh ₃ ) ₄ (0.97 g, 0.84 mmol), K ₂ CO ₃ (4.66 g, 33.75 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-4 (8.48 g, yield 72%) was obtained by column chromatography.

[LCMS]: 697

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-4, C-4, D-4, E-4, F-4, G-4, respectively , H-4 can be synthesized.

[Synthesis Example 5] Synthesis of compound A-5

The compound of the preparation example is the target compound (10g, 18.10mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.84 g, 18.10 mmol) and Pd(PPh ₃ ) ₄ (1.05 g, 0.9 mmol), K ₂ CO ₃ (5 g, 36.19 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-5 (8.57 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-5, C-5, D-5, E-5, F-5, G-5, respectively , H-5 can be synthesized.

[Synthesis Example 6] Synthesis of compound A-6

The compound of the preparation example is the target compound (10g, 18.10mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.84 g, 18.10 mmol) and Pd(PPh ₃ ) ₄ (1.05 g, 0.9 mmol), K ₂ CO ₃ (5 g, 36.19 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-6 (8.57 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-6, C-6, D-6, E-6, F-6, G-6, respectively , H-6 can be synthesized.

[Synthesis Example 7] Synthesis of compound A-7

The compound of the preparation example is the target compound (10g, 16.87mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.52 g, 16.87 mmol) and Pd(PPh ₃ ) ₄ (0.97 g, 0.84 mmol), K ₂ CO ₃ (4.66 g, 33.75 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-3 (8.48 g, yield 72%) was obtained by column chromatography.

[LCMS]: 697

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-7, C-7, D-7, E-7, F-7, G-7, respectively , H-7 can be synthesized.

[Synthesis Example 8] Synthesis of compound A-8

The compound of the preparation example is the target compound (10g, 16.87mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.52 g, 16.87 mmol) and Pd(PPh ₃ ) ₄ (0.97 g, 0.84 mmol), K ₂ CO ₃ (4.66 g, 33.75 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-4 (8.48 g, yield 72%) was obtained by column chromatography.

[LCMS]: 697

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-8, C-8, D-8, E-8, F-8, G-8, respectively , H-8 can be synthesized.

[Synthesis Example 9] Synthesis of compound A-9

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-9 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-9, C-9, D-9, E-9, F-9, G-9, respectively , H-9 can be synthesized.

[Synthesis Example 10] Synthesis of compound A-10

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-10 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-10, C-10, D-10, E-10, F-10, G-10, respectively , H-10 can be synthesized.

[Synthesis Example 11] Synthesis of compound A-11

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-11 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-11, C-11, D-11, E-11, F-11, G-11, respectively , H-11 can be synthesized.

[Synthesis Example 12] Synthesis of compound A-12

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-12 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-12, C-12, D-12, E-12, F-12, G-12, respectively , H-12 can be synthesized.

[Synthesis Example 13] Synthesis of compound A-13

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-13 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-13, C-13, D-13, E-13, F-13, G-13 , H-13 can be synthesized.

[Synthesis Example 14] Synthesis of compound A-14

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-14 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-14, C-14, D-14, E-14, F-14, G-14, respectively , H-14 can be synthesized.

[Synthesis Example 15] Synthesis of compound A-15

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-15 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-15, C-15, D-15, E-15, F-15, G-15, respectively , H-15 can be synthesized.

[Synthesis Example 16] Synthesis of compound A-16

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-16 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-16, C-16, D-16, E-16, F-16, G-16, respectively , H-16 can be synthesized.

[Synthesis Example 17] Synthesis of compound A-17

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-17 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-17, C-17, D-17, E-17, F-17, G-17, respectively , H-17 can be synthesized.

[Synthesis Example 18] Synthesis of compound A-18

The compound of the preparation example is the target compound (10g, 17.93 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.80 g, 17.93 mmol) and Pd(PPh ₃ ) ₄ (1.04 g, 0.90 mmol), K ₂ CO ₃ (4.96 g, 35.87 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-18 (8.82 g, yield 72%) was obtained by column chromatography.

[LCMS]: 682

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-18, C-18, D-18, E-18, F-18, G-18, respectively , H-18 can be synthesized.

[Synthesis Example 19] Synthesis of compound A-19

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-19 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-19, C-19, D-19, E-19, F-19, G-19, respectively , H-19 can be synthesized.

[Synthesis Example 20] Synthesis of compound A-20

The compound of the preparation example is the target compound (10g, 16.19 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.33 g, 16.19 mmol) and Pd(PPh ₃ ) ₄ (0.94 g, 0.81 mmol), K ₂ CO ₃ (4.48 g, 32.38 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-20 (8.43 g, yield 72%) was obtained by column chromatography.

[LCMS] : 722

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-20, C-20, D-20, E-20, F-20, G-20, respectively , H-20 can be synthesized.

[Synthesis Example 21] Synthesis of compound A-21

The compound of the preparation example is the target compound (10g, 21.67 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (5.8 g, 21.67 mmol) and Pd(PPh ₃ ) ₄ (1.25 g, 1.08 mmol), K ₂ CO ₃ (5.99 g, 43.35 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-21 (8.84 g, yield 72%) was obtained by column chromatography.

[LCMS]: 566

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-21, C-21, D-21, E-21, F-21, G-21, respectively , H-21 can be synthesized.

In addition, the prepared compound was 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) Use 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)benzonitrile instead of benzonitrile 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-24, B-24, C-24, D-24, E-24, F-24, G -24 and H-24 can be synthesized.

In addition, the prepared compound was 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) Use 4-(3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)benzonitrile instead of benzonitrile 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-27, B-27, C-27, D-27, E-27, F-27, G -27 and H-27 can be synthesized.

[Synthesis Example 22] Synthesis of compound A-22

Prepare the compound of the preparation example with the target compound (10g, 20.51 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (5.49 g, 20.51 mmol) and Pd(PPh ₃ ) ₄ (1.19 g, 1.03 mmol), K ₂ CO ₃ (5.67 g, 41.03 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-22 (8.84 g, yield 72%) was obtained by column chromatography.

[LCMS]: 592

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-22, C-22, D-22, E-22, F-22, G-22, respectively , H-22 can be synthesized.

In addition, the prepared compound was 8-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) 8-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline instead of quinoline 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-25, B-25, C-25, D-25, E-25, F-25, G -25 and H-25 can be synthesized.

In addition, the prepared compound was 8-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) 8-(3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline instead of quinoline 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-28, B-28, C-28, D-28, E-28, F-28, G -28 and H-28 can be synthesized.

[Synthesis Example 23] Synthesis of compound A-23

Prepare the compound of the preparation example with the target compound (10g, 20.51 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (5.49 g, 20.51 mmol) and Pd(PPh ₃ ) ₄ (1.19 g, 1.03 mmol), K ₂ CO ₃ (5.67 g, 41.03 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-23 (8.84 g, yield 72%) was obtained by column chromatography.

[LCMS]: 592

As in the above synthesis method, 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine 6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6 -triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d] When using pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, B-23, C-23, D-23, E-23, F-23, G-23, respectively , H-23 can be synthesized.

In addition, the prepared compound was 5-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) 5-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline instead of quinoline 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-26, B-26, C-26, D-26, E-26, F-26, G -26 and H-26 can be synthesized.

In addition, the prepared compound was 5-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl) 5-(3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)quinoline instead of quinoline 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6- chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or When using 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, A-29, B-29, C-29, D-29, E-29, F-29, G -29 and H-29 can be synthesized.

[Synthesis Example 24] Synthesis of compound A-30

The compound of the preparation example is the target compound (10g, 16.90 mmol) obtained through Miyaura Borylation Reaction, 2-chloro-4,6-diphenyl-1,3,5-triazine (4.53 g, 16.90 mmol) and Pd(PPh ₃ ) ₄ (0.98 g, 0.85 mmol), K ₂ CO ₃ (4.67 g, 33.81 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-30 (8.48 g, yield 72%) was obtained by column chromatography.

[LCMS]: 696

2,4-diphenyl-6-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren as in the above synthesis method ]-7'-yl)-1,3,5-triazine instead of 2,4-diphenyl-6-(3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) )spiro[cyclohexane-1,9'-fluoren]-7'-yl)-1,3,5-triazine or 2,4-diphenyl-6-(3'-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-6'-yl)-1,3,5-triazine was used, and 2-chloro-4,6-diphenyl -1,3,5-triazine instead of 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine or 2-([1, 1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[ 1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine or 2-chloro-4-phenylbenzo[4,5] If thieno[2,3-d]pyrimidine is used, A-30~68 can be synthesized, respectively.

In the same way, 2,4-diphenyl-6-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren] Instead of -7'-yl)-1,3,5-triazine, 2,4-diphenyl-6-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) )spiro[cyclohexane-1,9'-fluoren]-7'-yl)pyrimidine or 4-([1,1'-biphenyl]-4-yl)-2-phenyl-6-(2'-(4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)pyrimidine or 2,3,5-triphenyl-6-( 2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)pyrazine or 6,8-diphenyl -2-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)-[1 ,2,4]triazolo[1,5-a]pyridine or 2-phenyl-4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[ cyclohexane-1,9'-fluoren]-7'-yl)benzo[4,5]thieno[3,2-d]pyrimidine or 4-phenyl-2-(2'-(4,4,5,5- Preparation compounds such as tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)benzo[4,5]thieno[2,3-d]pyrimidine and 2-chloro-4,6-diphenyl-1,3,5-triazine or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1' -biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-3,5,6-triphenylpyrazine or 2-chloro-6,8-diphenyl-[1,2,4]triazolo[1,5-a]pyridine or 4-chloro-2-phenylbenzo[4,5 When using ]thieno[3,2-d]pyrimidine or 2-chloro-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine, I-1~16, J-1~18, K- 1 to 30 can be synthesized.

* Device example (device evaluation result)

[Examples 1-39] Preparation of green organic EL device

Compounds A-17~23, B-17~20, C-17~23, D-17~23, E-17~23, G-17~23 are purified by sublimation with high purity by a commonly known method, and then A green organic EL device was fabricated according to the procedure.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and vacuum evaporator The substrate was transferred to

On the prepared ITO transparent electrode, m-MTDATA (60 nm)/TCTA (80 nm)/ A-17~23, B-17~20, C-17~23, D-17~23, E-17~23, Each compound of G-17~23 + 10% Ir(ppy) ₃ (30 nm)/BCP (10 nm)/Alq ₃ (30 nm)/LiF (1 nm)/Al (200 nm) layered in order An EL device was fabricated.

The structures of m-MTDATA, TCTA, Ir(ppy) ₃ , CBP and BCP are as follows.

[Comparative Example 1] Preparation of green organic EL device

A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound A-17 as a light emitting host material when the light emitting layer was formed.

[Evaluation Example 1]

For each green organic EL device manufactured in Examples 1 to 39 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of (10) mA/cm 2 were measured, and the results are shown in Table 1 below. it was

Sample host drive voltage
(V) EL peak
(nm) current efficiency
(cd/A) Example 1 A-17 5.43 515 44.2 Example 2 A-18 5.52 516 42.2 Example 3 A-19 5.44 516 49.2 Example 4 A-20 5.54 517 44.7 Example 5 A-21 5.34 518 45.2 Example 6 A-22 5.69 516 43.5 Example 7 A-23 5.43 515 44.2 Example 8 B-17 5.55 517 42.3 Example 9 B-18 5.44 518 49.1 Example 10 B-19 5.53 517 44.8 Example 11 B-20 5.35 517 45.4 Example 12 C-17 5.69 516 43.6 Example 13 C-18 5.43 515 44.2 Example 14 C-19 5.52 516 42.2 Example 15 C-20 5.34 518 45.2 Example 16 C-21 5.69 516 43.5 Example 17 C-22 5.43 515 44.2 Example 18 C-23 5.69 516 43.5 Example 19 D-17 5.43 515 44.2 Example 20 D-18 5.43 515 44.2 Example 21 D-19 5.52 516 42.2 Example 22 D-20 5.44 516 49.2 Example 23 D-21 5.35 517 45.4 Example 24 D-22 5.69 516 43.6 Example 25 D-23 5.43 515 44.2 Example 26 E-17 5.52 516 42.2 Example 27 E-18 5.44 516 49.2 Example 28 E-19 5.34 518 45.2 Example 29 E-20 5.69 516 43.5 Example 30 E-21 5.43 515 44.2 Example 31 E-22 5.35 517 45.4 Example 32 E-23 5.55 517 42.3 Example 33 G-17 5.44 518 49.1 Example 34 G-18 5.53 517 44.8 Example 35 G-19 5.43 515 44.2 Example 36 G-20 5.52 516 42.2 Example 37 G-21 5.44 516 49.2 Example 38 G-22 5.34 518 45.2 Example 39 G-23 5.69 516 43.5 Comparative Example 1 CBP 6.52 516 38.2

As shown in Table 1 above, compounds A-17 to 23, B-17 to 20, C-17 to 23, D-17 to 23, E-17 to 23, G-17 to 23 according to the present invention are green When used as a light emitting layer of an organic EL device (Examples 1 to 39), it can be seen that compared to a green organic EL device using conventional CBP (Comparative Example 1), it shows better performance in terms of efficiency and driving voltage.

[Examples 40 to 142] Fabrication of blue organic electroluminescent device

Compounds synthesized in Synthesis Example A-9 to 73, B-13 to 20, C-9 to 29, D-17 to 23, E-17 to 23, G-17 to 29, I-2 to 13, J- After high-purity sublimation purification of 2 to 17 and K-1 to 9 by a commonly known method, a blue organic electroluminescent device was manufactured as follows.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. The substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (Doosan Electronics, 30 nm)/Compounds A-9 to 73, B -13 ~ 20, C-9 ~ 29, D-17 ~ 23, E-17 ~ 23, G-17 ~ 29, I-2 ~ 13, J-2 ~ 17, K-1 ~ 9 each compound ( 30 nm)/LiF (1 nm)/Al (200 nm) were stacked in the order to fabricate an organic electroluminescent device.

[Comparative Example 2] Fabrication of a blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 40, except that Alq3 was used instead of Compound A-9 as the electron transport layer material.

[Comparative Example 3] Fabrication of a blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 40, except that Compound A-9 was not used as the electron transport layer material.

The structures of NPB, AND, and Alq3 used in Examples 40 to 142 and Comparative Examples 2 and 3 are as follows.

[Evaluation Example 2]

For each of the blue organic electroluminescent devices manufactured in Examples 40 to 142 and Comparative Examples 2 and 3, the driving voltage, current efficiency and emission peak at a current density (10) mA/cm 2 were measured, and the results are shown in the table below 2 is shown.

Sample material drive voltage
(V) EL peak
(nm) current efficiency
(cd/A) Example 40 A-9 3.6 456 6.6 Example 41 A-10 3.7 456 6.5 Example 42 A-11 3.7 458 6.6 Example 43 A-12 4.1 453 6.5 Example 44 A-13 3.8 456 6.8 Example 45 A-14 4.0 457 6.6 Example 46 A-15 3.6 456 6.6 Example 47 A-16 3.6 456 6.6 Example 48 A-17 3.7 456 6.5 Example 49 A-18 3.6 458 6.6 Example 50 A-19 4.1 453 6.5 Example 51 A-20 4.1 453 6.5 Example 52 A-21 3.8 456 6.8 Example 53 A-22 4.0 457 6.6 Example 54 A-23 3.6 456 6.6 Example 55 A-24 3.8 456 6.8 Example 56 A-25 3.8 456 6.8 Example 57 A-26 3.6 456 6.6 Example 58 A-27 3.6 456 6.6 Example 59 A-28 3.7 456 6.5 Example 60 A-29 3.7 458 6.6 Example 61 A-30 4.1 453 6.5 Example 62 A-34 4.1 453 6.5 Example 63 A-37 3.8 456 6.8 Example 64 A-39 4.0 457 6.6 Example 65 A-41 3.6 456 6.6 Example 66 A-45 4.1 453 6.5 Example 67 A-47 3.8 456 6.8 Example 68 A-49 3.8 456 6.8 Example 69 A-51 4.0 457 6.6 Example 70 A-46 4.0 457 6.6 Example 71 A-57 3.8 456 6.8 Example 72 A-59 4.1 453 6.5 Example 73 A-61 4.1 453 6.5 Example 74 A-65 3.8 456 6.8 Example 75 A-67 4.0 457 6.6 Example 76 A-73 3.6 456 6.6 Example 77 B-13 3.8 456 6.8 Example 78 B-15 4.0 457 6.6 Example 79 B-17 3.8 456 6.8 Example 80 B-18 4.1 453 6.5 Example 81 B-19 3.8 456 6.8 Example 82 B-20 4.0 457 6.6 Example 83 C-9 4.0 457 6.6 Example 84 C-11 4.1 453 6.5 Example 85 C-13 3.8 456 6.8 Example 86 C-15 4.0 457 6.6 Example 87 C-17 3.6 456 6.6 Example 88 C-18 3.8 456 6.8 Example 89 C-19 4.0 457 6.6 Example 90 C-20 3.6 456 6.6 Example 91 C-21 4.1 453 6.5 Example 92 C-22 3.8 456 6.8 Example 93 C-23 3.8 456 6.8 Example 94 C-24 4.0 457 6.6 Example 95 C-25 3.6 456 6.6 Example 96 C-26 4.1 453 6.5 Example 97 C-27 3.8 456 6.8 Example 98 C-28 4.0 457 6.6 Example 99 C-29 3.6 456 6.6 Example 100 D-17 3.7 456 6.5 Example 101 D-18 3.7 458 6.6 Example 102 D-19 4.1 453 6.5 Example 103 D-20 3.8 456 6.8 Example 104 D-21 4.0 457 6.6 Example 105 D-22 3.7 456 6.5 Example 106 D-23 4.1 453 6.5 Example 107 E-9 3.8 456 6.8 Example 108 E-11 4.0 457 6.6 Example 109 E-17 3.6 456 6.6 Example 110 E-18 3.6 456 6.6 Example 111 E-19 3.7 456 6.5 Example 112 E-20 3.7 458 6.6 Example 113 E-21 4.1 453 6.5 Example 114 E-22 3.8 456 6.8 Example 115 E-23 4.0 457 6.6 Example 116 E-13 3.6 456 6.6 Example 117 E-15 3.7 456 6.5 Example 118 G-9 3.7 458 6.6 Example 119 G-11 4.1 453 6.5 Example 120 G-13 3.8 456 6.8 Example 121 G-15 4.0 457 6.6 Example 122 G-17 3.7 458 6.6 Example 123 G-18 4.1 453 6.5 Example 124 G-19 3.7 458 6.6 Example 125 G-20 4.1 453 6.5 Example 126 G-21 3.8 456 6.8 Example 127 G-22 4.0 457 6.6 Example 128 G-23 3.7 458 6.6 Example 129 G-27 4.1 453 6.5 Example 130 G-28 3.8 456 6.8 Example 131 G-29 4.1 453 6.5 Example 132 I-2 3.8 456 6.8 Example 133 I-5 4.0 457 6.6 Example 134 I-7 3.6 456 6.6 Example 135 I-9 4.1 453 6.5 Example 136 I-13 3.7 458 6.6 Example 137 J-2 4.1 453 6.5 Example 138 J-8 3.8 456 6.8 Example 139 J-9 4.0 457 6.6 Example 140 J-17 3.6 456 6.6 Example 141 K-1 3.7 456 6.5 Example 142 K-9 3.7 458 6.6 Comparative Example 2 Alq ₃ 4.7 459 5.6 Comparative Example 3 - 4.8 460 6.2

As shown in Table 2, the blue organic electroluminescent device (Examples 40 to 142) using the compound of the present invention for the electron transport layer was a blue organic electroluminescent device using the conventional Alq3 for the electron transport layer (Comparative Example 2) and electron It was found that the blue organic EL device without a transport layer (Comparative Example 3) exhibited superior performance in terms of driving voltage, emission peak and current efficiency.

[Examples 143 to 168] Preparation of blue organic electroluminescent device

After high-purity sublimation purification of the compound synthesized in Synthesis Examples A-1~8, C-1~4, E-1~4, F-1~4, G-5~8 by a conventionally known method, According to the process, a blue organic electroluminescent device was manufactured.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. 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 (Doosan Electronics, 30 nm) / A-1~8, C-1~4, E-1~4, F-1~4, G-5~8 (5 nm) / Alq3 (25 nm) / LiF (1 nm) / Al (200 nm) were stacked in the order to prepare an organic electroluminescent device. .

The structures of NPB, ADN and Alq3 used at this time are as follows.

[Comparative Example 4] Preparation of blue organic electroluminescent device

In Example 143, the same procedure as in Example 143 was performed, except that Compound A-1 used as an electron transport auxiliary layer material was not used, and Alq3, an electron transport layer material, was deposited at 30 nm instead of 25 nm. An electroluminescent device was fabricated.

[Evaluation Example 3]

For the organic electroluminescent devices prepared in Examples 143 to 168 and Comparative Example 4, respectively, the driving voltage, emission wavelength, current efficiency, and emission wavelength at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 3 below. indicated.

Sample electron transport auxiliary layer drive voltage
(V) luminescence peak
(nm) Current efficiency (cd/A) Example 143 A-1 3.6 456 6.6 Example 144 A-2 3.7 456 6.5 Example 145 A-3 3.7 458 6.6 Example 146 A-4 4.1 453 6.5 Example 147 A-5 3.8 456 6.8 Example 148 A-6 3.6 456 6.6 Example 149 A-7 3.7 456 6.5 Example 150 A-8 3.7 458 6.6 Example 151 C-1 4.1 453 6.5 Example 152 C-2 3.8 456 6.8 Example 153 C-3 3.7 458 6.6 Example 154 C-4 4.1 453 6.5 Example 155 E-1 3.8 456 6.8 Example 156 E-2 3.6 456 6.6 Example 157 E-3 3.7 456 6.7 Example 158 E-4 3.6 456 6.6 Example 159 F-1 3.7 456 6.5 Example 160 F-2 4.1 453 6.5 Example 161 F-3 3.8 456 6.8 Example 162 F-4 3.6 456 6.8 Example 163 G-1 3.6 456 6.6 Example 164 G-2 3.7 456 6.5 Example 165 G-5 3.6 458 6.6 Example 166 G-6 4.1 453 6.5 Example 167 G-7 3.8 456 6.8 Example 168 G-8 3.6 456 6.6 Comparative Example 4 - 4.8 457 5.8

As shown in Table 3, the blue organic electroluminescent device of Examples 143 to 168 including an electron transport auxiliary layer formed of the compound according to the present invention is Comparative Example 4 comprising an electron transport layer made of Alq3 without an electron transport auxiliary layer It was found that the organic electroluminescent device exhibited superior performance in terms of current efficiency and driving voltage.

10: positive electrode 20: negative electrode
30: organic layer 31: hole transport layer
32: light emitting layer 33: hole transport auxiliary layer
34: electron transport layer 35: electron transport auxiliary layer
36: electron injection layer 37: hole injection layer

Claims (11)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
n is an integer from 0 to 3,
A and B are each independently a substituent represented by any one of the following Chemical Formulas 2 to 4,
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4,
* is the part where the bond is made,
A plurality of Xs are the same or different from each other, and each independently C (R) or N, but X represented by Formula 2 and Formula 3 represented by A is at least two or more N,
R is hydrogen, deuterium, halogen, cyano group, nitro group, C1~ C40 alkyl group, C2~ C4 ₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, 3 nuclear atoms to 40 heterocycloalkyl 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 ₃ ~ 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 ₆ ~ mono or diaryl phosphine of C ₆₀ blood group and a C ₆ ~ C is selected from the ₆₀ group consisting of aryl amines, form a condensed ring of the group aliphatic, aromatic, aliphatic hetero, or aromatic heterocyclic group which are adjacent to each other, or to achieve a spiro bond there is,
R of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, an aryl group Phosphine group, mono or diarylphosphinyl group and arylsilyl group are 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 ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl Amine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C substituted with at least ₆₀ of the aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ selected from the group consisting arylsilyl of C ₆₀ one kind of substituent or being unsubstituted , when substituted with a plurality of substituents, they may be the same or different from each other,
m is an integer from 1 to 3,
When Ar1 is plural, it is the same or different from each other, and each independently is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, It is a substituted or unsubstituted heteroaryl group, and may form a condensed ring with adjacent X,
Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. According to claim 1,
Formula 2 is a compound, characterized in that selected from the group consisting of Formulas 5 to 10:
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 5 to 10,
* is the part where the bond is made,
Y is hydrogen, deuterium, halogen, cyano group, nitro group, C1~ C40 alkyl group, C2~ C4 ₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, 3 nuclear atoms to 40 heterocycloalkyl 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 ₃ ~ 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 ₆ ~ of C ₆₀ mono or diaryl phosphine group P is selected from the group consisting of C ₆ ~ C ₆₀ aryl amine,
X and Ar1 are each as defined in claim 1. According to claim 1,
Formula 3 is a compound characterized in that the formula 11:
[Formula 12]

In the above formula (11),
* is the part where the bond is made,
X is as defined in claim 1. According to claim 1,
Formula 4 is a compound characterized in that it is Formula 12 or Formula 13:
[Formula 12]

[Formula 13]

In the above formulas 12 to 13,
* is the part where the bond is made,
X is as defined in claim 1. 3. The method of claim 2,
Formula 5 is a compound characterized in that it is represented by Formula 14 or Formula 15:
[Formula 14]

[Formula 15]

In Formula 14 or Formula 15,
* is the part where the bond is made,
Ar1 is as defined in claim 1. 3. The method of claim 2,
Formula 6 is a compound characterized in that the following formula 16:
[Formula 16]

In the formula (16),
* is the part where the bond is made,
Ar1 is as defined in claim 1. 3. The method of claim 2,
Formula 4 is a compound characterized in that the following formula 17:
[Formula 17]

In Formula 17,
* is the part where the connection is made. According to claim 1,
L is a single bond or a compound characterized in that it is a linker selected from the following L-1 to L-3:

In L-1 to L-3,
* is the part where the connection is made. According to claim 1,
The compound is a compound characterized in that it is selected from the group consisting of:

An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound represented by the formula (1) of claim 1. 11. The method of claim 10,
The organic material layer is an organic electroluminescent device comprising one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and a light emitting layer.

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