KR102156494B1 - Organometallic compound and organic light emitting device comprising same - Google Patents

Abstract

The present specification provides an organometallic compound represented by Chemical Formula 1 and an organic light emitting device including the same.

Description

Organometallic compound and organic light emitting device including the same {ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME}

The present invention relates to an organometallic compound represented by Chemical Formula 1 and an organic light-emitting device including the same.

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0027342 filed with the Korean Intellectual Property Office on March 8, 2018, the entire contents of which are incorporated herein.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer has a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

Korean Patent Application Publication No. 10-2008-0109671

An object of the present specification is to provide an organic light-emitting device having good efficiency, driving voltage and/or light emission characteristics, and good color purity.

The present specification provides an organometallic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is NR, O, S or Se,

X1 is N or CRa, X2 is N or CRb, X3 is N or CRc, X4 is N or CRd, and at least two of X1 to X4 are N,

R and Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted heteroaralkyl group; Or a substituted or unsubstituted aryl group,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted heteroaralkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted cycloalkenyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n is 1 or 2,

a1 is an integer of 0 to 4, and if a1 is 2 or more, R1 is the same as or different from each other,

a2 is an integer of 0 to 2, and if a2 is 2, R2 is the same as or different from each other,

a3 is an integer from 0 to 4, and if a3 is 2 or more, R3 is the same as or different from each other,

a4 is an integer of 0 to 4, and when a4 is 2 or more, R4 is the same as or different from each other.

In addition, an exemplary embodiment of the present specification is an organic light-emitting device including a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode, wherein the organic metal compound is It provides an organic light emitting device that is included in one or more organic material layers provided between the first electrode and the second electrode.

The organometallic compound according to the present application includes a heterocycle containing 2 or more N in the compound, and an iridium metal, so that when used in an organic material layer of an organic light emitting device, particularly a light emitting layer, the device can emit vivid green light.

In some exemplary embodiments, the efficiency of the organic light-emitting device including the compound of the present invention is improved.

In some embodiments, the driving voltage of the organic light-emitting device including the compound of the present invention is lowered.

In some embodiments, the lifespan characteristics of the organic light-emitting device including the compound of the present invention are improved.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, a hole blocking layer 9, an electron transport layer 8 and a cathode 4 An example of an organic light emitting device is shown.

Hereinafter, the present invention will be described in more detail.

Examples of the substituents are described below, but are not limited thereto.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site bonded to another substituent or a bonding portion.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Amino group; Alkyl group; Cycloalkyl group; Aralkyl group; Alkoxy group; Alkenyl group; Phosphine oxide group; Phosphine group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxy group; Aryl group; And a heteroaryl group substituted or unsubstituted with one or more substituents selected from the group consisting of, or substituted or unsubstituted with a group to which two or more substituents are connected among the substituents selected from the group. For example, the arylalkenyl group may be an alkenyl group, or an aryl group may be interpreted as a substituted alkenyl group. Examples of the group to which three substituents are connected include an aryl group substituted with a heteroaryl group substituted with an aryl group, an aryl group substituted with an aryl group substituted with a heteroaryl group, and a heteroaryl group substituted with an aryl group substituted with a heteroaryl group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkoxy group refers to a group in which an alkyl group is bonded to an oxygen atom, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. According to an exemplary embodiment, the alkoxy group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkoxy group has 1 to 6 carbon atoms. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an iso-amyloxy group, and a hexyloxy group.

In the present specification, the silyl group may be represented by the formula of -SiRxRyRz, and Rx, Ry, and Rz are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group and phenylsilyl group, but is not limited thereto. Does not.

In the present specification, the aryloxy group refers to a group in which an aryl group is bonded to an oxygen atom, and the number of carbon atoms is not particularly limited, but is preferably 6 to 40. According to an exemplary embodiment, the aryloxy group has 6 to 30 carbon atoms. Specific examples of the aryloxy group include phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3-biphenyloxy group, 1- Naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 2-anthracenyloxy group, 9-anthracenyloxy group, 1-phenanthrenyloxy group, 3-phenanthrenyloxy group, 9-phenanthrenyloxy group There are times and so on.

In the present specification, the alkylphosphine group refers to a phosphine group substituted with an alkyl group. The number of carbon atoms of the alkylphosphine group is not particularly limited, but is preferably 1 to 20. Examples of the alkylphosphine group include dimethylphosphine group, diethylphosphine group, di-n-propylphosphine group, diisopropylphosphine group, di-n-butylphosphine group, di-sec-butylphosphine group, di-tert -Butylphosphine group, diisobutylphosphine group, tert-butylisopropylphosphine group, di-n-hexylphosphine group, di-n-octylphosphine group, di-n-mesylphosphine group, etc., but are not limited thereto. .

In the present specification, the arylphosphine group refers to a phosphine group substituted with an aryl group. The number of carbon atoms of the arylphosphine group is not particularly limited, but is preferably 6 to 30. Examples of the arylphosphine group include, but are not limited to, diphenylphosphine group, dibenzylphosphine group, methylphenylphosphine group, and benzylhexylphosphine group.

In the present specification, the alkyl group refers to a linear or branched chain hydrocarbon group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, octyl, n-octyl , tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl , 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group refers to a cyclic hydrocarbon group, and the number of carbon atoms is not particularly limited, but is preferably 3 to 60. According to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group represents a linear or ground unsaturated hydrocarbon group including a carbon-carbon double bond, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to an exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. Specific examples include, but are not limited to, ethenyl, vinyl, propenyl, allyl, isopropenyl, butenyl, isobutenyl, n-pentenyl and n-hexenyl.

In the present specification, the cycloalkenyl group represents a cyclic unsaturated hydrocarbon group including a carbon-carbon double bond, and the number of carbon atoms is not particularly limited, but is preferably 2 to 36. According to an exemplary embodiment, the number of carbon atoms of the cycloalkenyl group is 2 to 24. According to an exemplary embodiment, the cycloalkenyl group has 2 to 12 carbon atoms. Specific examples include, but are not limited to, cyclobutenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, norbornenyl, bicyclo[2.2.2]octenyl, and the like.

In the present specification, an aralkenyl group means an alkenyl group substituted with an aryl group.

In the present specification, an aryl group means wholly or partially unsaturated substituted or unsubstituted monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 40 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, and a terphenyl group, but are not limited thereto. The polycyclic aryl group is a naphthyl group, anthracenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, pyrenyl group, tetrasenyl group, chrysenyl group, pentacenyl group , Fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, and the like, but are not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

,

,

,

,

,

및

등이 있으나, 이에 한정되지 않는다.The substituted fluorenyl group is

,

,

,

,

,

,

And

And the like, but are not limited thereto.

In the present specification, the heteroaryl group is an aromatic ring group containing at least one of N, O, and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 2 to 30 carbon atoms. According to another exemplary embodiment, the heteroaryl group has 2 to 20 carbon atoms. Examples of heteroaryl groups include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, pyrimidyl group, tria Genyl group, triazolyl group, acridinyl group, carbolinyl group, acenaphthoquinoxalinyl group, indenoquinazolinyl group, indenoisoquinolinyl group, indenoquinolinyl group, pyridoindolyl group, pyzinyl group, pyra Genyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, Benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, phenanthrolinyl group (phenanthroline), thiazolyl group, isoxazolyl group , Oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenoxazinyl group, phenothiazinyl group, and dibenzofuranyl group, etc., but are not limited thereto. The heteroaryl group includes an aliphatic heteroaryl group and an aromatic heteroaryl group.

The above description of the alkyl group may be applied to the alkyl group in the aralkyl group, alkyl thioxy group, alkyl sulfoxy group and alkylaryl group.

The description of the aryl group described above may be applied to the aryl group among the aralkenyl group, arylphosphine group, aryloxy group, arylthioxy group, and arylsulfoxy group.

The description of the above-described heteroaryl group may be applied to the heteroalkyl group in the heteroaralkyl group.

An exemplary embodiment of the present invention provides an organometallic compound represented by Chemical Formula 1.

In the present invention, at least two of X1 to X4 in Formula 1 are N. Since N is an atom having a greater electron withdrawing property than C, a structure containing two or more N among X1 to X4 has a lower energy level than a structure containing one or less N. In particular, in the case of the iridium complex of the present invention, the HOMO energy level is relatively lower than the LUMO energy level because the HOMO energy level is spread toward benzofuropyrimidine (for example, the structure in which X is O). Can be obtained. Accordingly, since the band gap increases, when the compound of the present invention is used in an organic material layer of a device, in particular, a light emitting layer, light in a deeper green region can be obtained.

In the exemplary embodiment of the present specification, X1 is N, X2 is CRb, X3 is N, and R4 is CRd.

In the exemplary embodiment of the present specification, X1 is CRa, X2 is N, X3 is CRc, and X4 is N.

In the exemplary embodiment of the present specification, R and Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group unsubstituted or substituted with deuterium or an alkyl group; A cycloalkyl group unsubstituted or substituted with deuterium; Or an aryl group unsubstituted or substituted with deuterium or an alkyl group.

In the exemplary embodiment of the present specification, R and Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted methyl group; A substituted or unsubstituted ethyl group; A substituted or unsubstituted n-propyl group; A substituted or unsubstituted isopropyl group; A substituted or unsubstituted n-butyl group; A substituted or unsubstituted isobutyl group; A substituted or unsubstituted sec-butyl group; A substituted or unsubstituted t-butyl group; A substituted or unsubstituted pentyl group; A substituted or unsubstituted iso-amyl group; A substituted or unsubstituted cyclopentyl group; A substituted or unsubstituted cyclohexyl group; Or a substituted or unsubstituted phenyl group.

In the exemplary embodiment of the present specification, R and Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A methyl group unsubstituted or substituted with deuterium; An ethyl group unsubstituted or substituted with deuterium; An isopropyl group unsubstituted or substituted with deuterium; A cyclopentyl group unsubstituted or substituted with deuterium; A cyclohexyl group unsubstituted or substituted with deuterium; Or a phenyl group unsubstituted or substituted with deuterium.

In the exemplary embodiment of the present specification, Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CH ₃ ; -CD ₃ ; -CD(CH ₃ ) ₂ ; -CH ₂ CH ₃ ; -CH(CH ₃ ) ₂ ; -C ₅ H ₉ ; -C ₆ H ₁₁ ; -(1-dC ₆ H ₁₀ ); Or -C ₆ H ₅ .

In the exemplary embodiment of the present specification, R is a phenyl group.

In the exemplary embodiment of the present specification, Ra and Rc are the same.

In the exemplary embodiment of the present specification, Rb and Rd are the same.

In the exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group unsubstituted or substituted with deuterium; A cycloalkyl group unsubstituted or substituted with deuterium; An alkenyl group unsubstituted or substituted with deuterium; An aralkyl group unsubstituted or substituted with deuterium; A silyl group substituted with a methyl group; Or an amino group.

In the exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 6 carbon atoms substituted or unsubstituted with deuterium; A cycloalkyl group having 1 to 8 carbon atoms substituted or unsubstituted with deuterium; Or a silyl group unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms.

In the exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CH ₃ ; -CD ₃ ; -CH(CH ₃ ) ₂ ; -Si(CH ₃ ) ₃ ; -C ₅ H ₉ ; Or -CD(CH ₃ ) ₂ .

In the exemplary embodiment of the present specification, a1 is an integer of 0 to 2.

In the exemplary embodiment of the present specification, a2 is 0.

In the exemplary embodiment of the present specification, a3 is an integer of 0 to 2.

In the exemplary embodiment of the present specification, a4 is 0 or 1.

In an exemplary embodiment of the present specification, n is 2.

In an exemplary embodiment of the present specification, n is 1.

는 서로 같거나 상이하고, 상기 n이 2 이면

는 서로 같거나 상이하다.In the exemplary embodiment of the present specification, if n is 1

Is the same as or different from each other, and if n is 2

Are the same or different from each other.

In an exemplary embodiment of the present invention, Formula 1 is represented by any one of the following Formulas 2-A to 2-F.

[Formula 2-A]

[Formula 2-B]

[Formula 2-C]

[Formula 2-D]

[Formula 2-E]

[Formula 2-F]

In the formulas 2-A to 2-F,

The definitions of X, X1 to X4, R1 to R4, a1 to a4, and n are as defined in Formula 1.

가 위치하는 경우 소자의 효율, 수명 등의 특성이 특히 좋다.In an exemplary embodiment of the present invention, Formula 1 is represented by any one of Formulas 2-A to 2-F. Of these, like formula 2-A

When is located, characteristics such as efficiency and lifetime of the device are particularly good.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 3-A.

[Formula 3-A]

In Formula 3-A,

The definitions of X, Ra, Rc, R1 to R4, a1 to a4, and n are as defined in Formula 1.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 3-B.

[Formula 3-B]

In Formula 3-B,

The definitions of X, Rb, Rd, R1 to R4, a1 to a4, and n are as defined in Formula 1.

In the present specification, two or more of X1 to X4 in Formula 1 are N. When two of X1 to X4 are N, N may exist at ortho, meta, and para positions. When two of the Ns are present in the meta position of each other, it is possible to effectively create an electron-deficient (π-deficient) structure, so that the HOMO energy level is lowered, and in particular, it can emit green light with good purity.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 1A.

[Formula 1A]

[Formula 1B]

In Formula 1A,

One of A1 to A4 is C that sigma-bonds with *1 in Formula 1B, and one is C that sigma-bonds with *2 in Formula 1B, and the other two are each independently CR2, but with *1 in Formula 1B Sigma-bonding C and *2 in Formula 1B and sigma-bonding C are adjacent to each other,

The definitions of X, X1 to X4, R1 to R4, a1, a3, and a4 and n are the same as defined in Formula 1,

R2 is the same as or different from each other.

In the exemplary embodiment of the present specification, when A1 is C that sigma-bonds with *1 in Formula 1B, A2 is C that sigma-bonds with *2 in Formula 1B, and X4 is N, at least one of X1 and X3 is N or X is N

In an exemplary embodiment of the present specification, Formula 1 is represented by any one of Formulas 2-A to 2-F,

In Formulas 2-A to 2-F, the definitions of X, X1 to X4, R1 to R4, a1 to a4, and n are as defined in Formula 1,

However, in Formula 2-A, when X4 is N, at least one of X1 and X3 is N or X is N.

In the exemplary embodiment of the present specification, the organometallic compound represented by Formula 1 is any one selected from the following compounds.

According to an exemplary embodiment of the present specification, the organometallic compound of Formula 1 described above may be prepared according to the following General Formula 1. However, the method for preparing the organometallic compound of Formula 1 is not limited to the following General Formula 1, and some synthesis steps may be replaced by other known synthesis methods.

[General Formula 1]

In the general formula 1, the definitions of R1 to R4, a1 to a4, X, and X1 to X4 are as defined in Chemical Formula 1.

The synthesis method of General Formula 1 is a method of preparing a compound in which n is 2 in Formula 1, and a compound in which n is 1 can also be prepared by using the method of synthesizing an auxiliary ligand twice with iridium in the manufacturing method. .

In the exemplary embodiment of the present specification, as an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode, the organic metal compound described above is It provides an organic light emitting device that is included in an organic material layer provided between the first electrode and the second electrode.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light-emitting device is not limited thereto, and may include fewer or more organic material layers.

In the exemplary embodiment of the present specification, the one or more organic material layers include at least one of an electron injection layer, an electron transport layer, and a layer that simultaneously injects and transports electrons, and the organometallic compound is the electron injection layer and the electron transport layer. And at least one of layers simultaneously injecting and transporting electrons.

In the exemplary embodiment of the present specification, the one or more organic material layers include at least one of a hole injection layer, a hole transport layer, and a layer for simultaneously transporting and injecting holes, and the organometallic compound is the hole injection layer and the hole It is included in at least one of a transport layer and a layer that simultaneously transports and injects holes.

In the exemplary embodiment of the present specification, the one or more organic material layers include an emission layer, and the organometallic compound is included in the emission layer.

In the exemplary embodiment of the present specification, the emission layer is a green emission layer.

In the exemplary embodiment of the present specification, the organometallic compound is included as a dopant in the emission layer.

In the exemplary embodiment of the present specification, the emission layer further includes at least one host compound. In one embodiment, the emission layer may include two or more host compounds.

In the exemplary embodiment of the present specification, the host compound is a condensed aromatic ring derivative or a heterocyclic compound.

In the exemplary embodiment of the present specification, the host compound is a carbazole derivative or a triazine derivative.

In the exemplary embodiment of the present specification, the host compound may be represented by Formula B below, but is not limited thereto.

[Formula B]

In Formula B,

Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

L1 is a direct bond; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

m is an integer from 0 to 8,

When m is 2 or more, Ar2 is the same as or different from each other.

In an exemplary embodiment of the present specification, Formula B is represented by the following Formula B-1.

[Formula B-1]

In the formula B-1,

The definitions of Ar1, Ar2 and L1 are as defined in Formula B,

Ar3 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar4 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

L2 is a direct bond; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

k and p are each independently an integer of 0 to 7,

When k is 2 or more, Ar2 is the same as or different from each other,

When p is 2 or more, Ar4 is the same as or different from each other.

In an exemplary embodiment of the present specification, Formula B is represented by the following Formula B-2.

In Formula B-2,

The definitions of Ar1, Ar2 and L1 are as defined in Formula B,

Ar5 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

Rm and Rn are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

q is an integer of 0 to 4, and if q is 2 or more, Ar5 is the same as or different from each other,

r is an integer from 0 to 10, and when r is 2 or more, Ar2 is the same as or different from each other.

In the exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C6-C30 heteroaryl group.

In the exemplary embodiment of the present specification, Ar1 is an aryl group unsubstituted or substituted with an aryl group or a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group.

In the exemplary embodiment of the present specification, Ar1 is a phenyl group; Biphenyl group; Or a phenyl group or a triazinyl group unsubstituted or substituted with a biphenyl group.

In the exemplary embodiment of the present specification, Ar3 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C6-C30 heteroaryl group.

In the exemplary embodiment of the present specification, Ar3 is an aryl group unsubstituted or substituted with an aryl group or a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group.

In the exemplary embodiment of the present specification, Ar3 is a phenyl group; Biphenyl group; Or a phenyl group or a triazinyl group unsubstituted or substituted with a biphenyl group.

In the exemplary embodiment of the present specification, Ar2 is hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or combined with an adjacent group to form a substituted or unsubstituted ring having 5 to 30 carbon atoms.

In the exemplary embodiment of the present specification, Ar2 is hydrogen; heavy hydrogen; Alkyl group; An aryl group unsubstituted or substituted with an aryl group or a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group, or combine with an adjacent group to form a ring unsubstituted or substituted with an alkyl group or an aryl group.

In the exemplary embodiment of the present specification, Ar2 is hydrogen; Methyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted carbazolyl group, or combined with an adjacent group to form an indene ring substituted or unsubstituted with a methyl group.

In the exemplary embodiment of the present specification, Ar2 is hydrogen; Or a carbazolyl group substituted with a biphenyl group, or combine with an adjacent group to form an indene ring substituted with a methyl group.

In the exemplary embodiment of the present specification, Ar4 is hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or combined with an adjacent group to form a substituted or unsubstituted ring having 5 to 30 carbon atoms.

In the exemplary embodiment of the present specification, Ar4 is hydrogen; heavy hydrogen; Alkyl group; An aryl group unsubstituted or substituted with an aryl group or a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group, or combine with an adjacent group to form a ring unsubstituted or substituted with an alkyl group or an aryl group.

In the exemplary embodiment of the present specification, Ar4 is hydrogen; Methyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted carbazolyl group, or combined with an adjacent group to form an indene ring substituted or unsubstituted with a methyl group.

In the exemplary embodiment of the present specification, Ar4 is hydrogen.

In the exemplary embodiment of the present specification, Ar5 is hydrogen.

In the exemplary embodiment of the present specification, L1 is a direct bond; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C2 to C20 heteroaryl group.

In the exemplary embodiment of the present specification, L1 is a direct bond; An aryl group unsubstituted or substituted with an aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.

In the exemplary embodiment of the present specification, L1 is a direct bond; Or a substituted or unsubstituted phenylene group.

In the exemplary embodiment of the present specification, L2 is a direct bond; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C2 to C20 heteroaryl group.

In the exemplary embodiment of the present specification, L2 is a direct bond; An aryl group unsubstituted or substituted with an aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.

In the exemplary embodiment of the present specification, L2 is a direct bond; Or a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present specification, Rm and Rn are hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C10 alkyl group; A substituted or unsubstituted aryl group having 6 to 25 carbon atoms; Or a substituted or unsubstituted C2 to C25 heteroaryl group.

In the exemplary embodiment of the present specification, Rm and Rn are each a methyl group.

In the exemplary embodiment of the present specification, m is 1.

In the exemplary embodiment of the present specification, k is 0.

In the exemplary embodiment of the present specification, p is 0.

In the exemplary embodiment of the present specification, r is 0.

In the exemplary embodiment of the present specification, q is 0.

In the exemplary embodiment of the present specification, the compound represented by Formula B is any one selected from the following structures.

In the exemplary embodiment of the present specification, the light emitting layer contains 5 parts by weight to 20 parts by weight of the dopant based on 100 parts by weight of the sum of the weight parts of the at least one host and the dopant. Included in parts by weight.

In the exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another embodiment, the organic light-emitting device may be an inverted type organic light-emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

The structure of the organic light emitting device according to the exemplary embodiment of the present specification is illustrated in FIGS. 1 to 3.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In such a structure, the organometallic compound of Formula 1 may be included in the emission layer.

2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the organometallic compound of Formula 1 may be included in the emission layer.

3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, a hole blocking layer 9, an electron transport layer 8 and a cathode 4 An example of an organic light emitting device is shown. In such a structure, the organometallic compound of Formula 1 may be included in the emission layer.

The organic light-emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound of the present specification, that is, the organometallic compound of Formula 1.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. In this case, by using a physical vapor deposition method (PVD, physical vapor deposition) such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate. It can be prepared by forming an anode, forming an organic material layer including a hole injection layer, a hole transport layer, an emission layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate. However, the manufacturing method is not limited thereto.

In addition, the organometallic compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable. It is preferable that the HOMO (Highest Occupied Molecular Orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer, and materials known in the art may be used. The electron blocking layer is a layer that prevents electrons from flowing into the light-emitting layer and controls the flow of holes flowing into the light-emitting layer to control the performance of the entire device. The electron blocking material is preferably a compound having the ability to prevent the inflow of electrons from the emission layer to the anode and to control the flow of holes injected into the emission layer or the emission material. In one embodiment, an arylamine-based organic material may be used as the electron blocking layer, but is not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamine group, and the styrylamine compound is substituted or unsubstituted. As a compound in which at least one arylvinyl group is substituted on the cyclic arylamine, a compound in which one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamine group are substituted or unsubstituted can be used. have. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

A hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used. The hole blocking layer is a layer that blocks the introduction of holes from the emission layer to the cathode and controls the electrons flowing into the emission layer to control the performance of the entire device. The hole blocking material is preferably a compound having the ability to prevent the inflow of holes from the light emitting layer to the cathode and control electrons injected into the light emitting layer or the light emitting material. As the hole blocking material, an appropriate material may be used according to the configuration of the organic material layer used in the device. The hole blocking layer is located between the emission layer and the cathode, and is preferably provided in direct contact with the emission layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer. Suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium and samarium, and in each case, an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons as the electron injection material, has an electron injection effect from the cathode, and has an excellent electron injection effect on the light emitting layer or the light emitting material, and is created in the light emitting layer A compound that prevents the transfer of the resulting excitons to the hole injection layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidenemethane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

[Production Example]

Preparation Example 1-1: Synthesis of Intermediates A1 and B1

(1) Preparation of intermediate A1

Dissolve 2-bromopyridine (30 g) and phenylboronic acid (1.1 eq) in tetrahydrofuran (300 ml) in a round bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution ( potassium carbonate solution) (150 ml) was added, tetrakis-(triphenylphosphine) palladium (3 mol%) was added, followed by heating and stirring at 70° C. for 3 hours. After the reaction was completed, the temperature was lowered, the aqueous layer was separated, and the solvent in the organic layer was removed. After dissolving with chloroform, washing with water, magnesium sulfate and acid clay were added, stirred, filtered, and concentrated under reduced pressure. Thereafter, compound A1 was prepared by column chromatography using a solution in which ethyl acetate and hexane were mixed in a volume ratio of 1:50 (22.4 g, yield 76%).

(2) Preparation of Intermediate 1-1a

In a nitrogen atmosphere, iridium chloride (1eq) and compound A1 (22 g, 2.5 eq) were added to 2-ethoxyethanol (1000 ml) and distilled water (330 ml) in a round bottom flask. Heated and stirred for hours. The temperature was lowered to room temperature, filtered, and washed with 2L of ethanol to prepare a solid compound 1-1a (21 g, yield 59%).

(3) Preparation of intermediate B1

Silver trifluorometalsulfonic acid salt (hereinafter, AgOTf) (1.3eq) containing 500 ml of intermediate 1-1a (10.2 g) and methylene chloride was dissolved in 250 ml of methanol, and the light was blocked. It was stirred at room temperature. After 24 hours, after filtering, the solvent of the filtered filtrate was blown off and toluene was precipitated to obtain compound B1 without further purification (yield 91%).

Preparation Example 1-2: Synthesis of Intermediates A2 and B2

(1) Preparation of intermediate A2

The compound in the same manner as in the method of preparing Intermediate A1, except that 2-bromo-5-methylpyridine (50 g) was used instead of 2-bromopyridine. A2 was prepared (26 g, 65% yield).

(2) Preparation of Intermediate 1-1b

The intermediate 1-1b was prepared in the same manner as the intermediate 1-1a except that intermediate A2 was used instead of intermediate A1 (20 g, yield 54%)

(3) Preparation of intermediate B2

Intermediate B2 was prepared in the same manner as in the method of preparing Intermediate B1, except that Intermediate 1-1b was used instead of Intermediate 1-1a (yield 64%).

Preparation Example 1-3: Synthesis of Intermediates A3 and B3

(1) Preparation of Intermediate 1-1c

Except for using 2,5-bromopyridine (2,5-bromopyridine) (55 g) instead of 2-bromopyridine (2-bromopyridine), compound 1-1c was prepared in the same manner as in the method of preparing Intermediate A1. Was prepared (30 g, yield 70%).

(2) Preparation of Intermediate 1-1d

Intermediate 1-1c (35 g) was dissolved in diethylether in a round bottom flask in a nitrogen atmosphere, and 2.5M n-BuLi (65 ml) was added at -78°C, followed by stirring for 1 hour. After adding triethylborate (2 eq) at -78 °C, the mixture was stirred at room temperature for 1 hour. 2M hydrochloride solution (100 ml) was added, stirred for 30 minutes, and then neutralized with 20% sodium hydroxide solution (100 ml). After separating the aqueous layer, the solvent in the organic layer was removed. Compound 1-1d was prepared by column chromatography using a solution in which hexane and ethyl acetate were mixed in a volume ratio of 100:1 (21 g, yield 73%).

(3) Preparation of intermediate A3

In a nitrogen atmosphere, intermediate 1-1d (21 g) and iodomethane-d3 (1.5 eq) were dissolved in tetrahydrofuran (200 ml) and methanol (100 ml) in a round bottom flask, and then 2M carbonic acid. Potassium carbonate solution (100ml) was added, tetrakis-(triphenylphosphine)palladium (3.8 g, 3.3 mmol) was added, followed by heating and stirring at 70° C. for 12 hours. After dissolving with chloroform, washing with water, magnesium sulfate and acid clay were added, stirred, filtered, and concentrated under reduced pressure. Thereafter, compound A3 was prepared by column chromatography using a solution in which hexane and ethyl acetate were mixed in a volume ratio of 50:1 (11 g, yield 67%).

(4) Preparation of Intermediate 1-1e

The intermediate 1-1e was prepared in the same manner as the intermediate 1-1a, except that intermediate A3 was used instead of intermediate A1 (10.2 g, yield 62%).

(5) Preparation of intermediate B3

The intermediate B3 was prepared in the same manner as the intermediate B1 except for using the intermediate 1-1e instead of the intermediate 1-1a (yield 90%).

Preparation Example 1-4: Synthesis of Intermediates A4 and B4

(1) Preparation of Intermediate 1-1f

2-bromo-5-methylpyridine (30 g, 0.17 mol) instead of 2-bromopyridine, para-tolylbo instead of phenylboronic acid Compound 1-1f was prepared in the same manner as the method of preparing Intermediate A1, except that p-tolylboronic acid (26 g, 0.19 mol) was used (22 g, yield 70%).

(2) Preparation of intermediate A4

In a nitrogen atmosphere, intermediate 1-1f (22 g, 0.12 mol) and sodium ethoxide (5.8 g, 0.085 mol) were dissolved in 300 ml of dimethylsulfoxide-d6 in a round bottom flask. It was heated and stirred at 80° C. for 32 hours. After lowering the temperature to room temperature, it was quenched with 100 ml (10 eq) of D ₂ O and sufficiently stirred for 1 hour. An excess of H ₂ O was added, extracted with ethyl acetate, and concentrated under reduced pressure. Thereafter, compound A4 was separated by column chromatography using a solution in which hexane and ethyl acetate were mixed in a volume ratio of 50:1. (10 g, yield 46%)

(3) Preparation of Intermediate 1-1g

The intermediate 1-1g was prepared in the same manner as the intermediate 1-1a except that intermediate A4 was used instead of intermediate A1 (10.4 g, yield 65%).

(5) Preparation of intermediate B4

Intermediate B4 was prepared in the same manner as the method of preparing Intermediate B1, except that Intermediate 1-1g was used instead of Intermediate 1-1a (yield 87%).

Preparation Example 1-5: Synthesis of Intermediates A5 and B5

(1) Preparation of intermediate 1-1h

2-bromopyridine (2-bromopyridine) instead of 2-bromo-4,5-dimethylpyridine (2-bromo-4,5-methylpyridine) (50 g, 0.27 mol), instead of phenylboronic acid (phenylboronic acid) Compound 1-1h was prepared in the same manner as in the method of preparing Intermediate A1 except for using para-tolylboronic acid (40 g, 0.30 mol) (35 g, yield 66%). .

(2) Preparation of intermediate A5

Intermediate A5 was prepared in the same manner as the method of preparing Intermediate A4, except that Intermediate 1-1h was used instead of Intermediate 1-1f (19 g, yield 58%).

(3) Preparation of Intermediate 1-1i

The intermediate 1-1i was prepared in the same manner as the intermediate 1-1a except that intermediate A5 was used instead of intermediate A1 (20 g, yield 55%).

(5) Preparation of intermediate B5

The intermediate B5 was prepared in the same manner as the intermediate B1 except for using the intermediate 1-1i instead of the intermediate 1-1a (yield 90%).

Preparation Example 1-6: Synthesis of Intermediates A6 and B6

(1) Preparation of intermediate A6

Except for using 2-bromo-4-cyclohexylpyridine (40 g) instead of 2-bromopyridine, Compound A6 was prepared in the same manner as in the method of preparing Intermediate A1 (49 g, Yield 50%).

(2) Preparation of Intermediate 1-1j

The intermediate 1-1j was prepared in the same manner as the intermediate 1-1a except that intermediate A6 was used instead of intermediate A1 (45 g, yield 54%)

(3) Preparation of intermediate B6

Intermediate B6 was prepared in the same manner as in the method of preparing Intermediate B1, except that Intermediate 1-1j was used instead of Intermediate 1-1a (yield 83%).

Manufacturing Example 2

Preparation Example 2-1: Synthesis of Intermediates C1 and D1

(1) Preparation of intermediate C1

In a nitrogen atmosphere, 2-bromopyridine (50 g), benzofuro[2,3-d]pyrimidin-8-ylboronic acid (1.2 eq) was added to tetrahydrofuran (400 g) in a round bottom flask. ml) and methanol (200 ml), 2M potassium carbonate solution (250 ml) was added, tetrakis-(triphenylphosphine) palladium (7.4 g, 6.4 mmol) was added. It was heated and stirred at 80° C. for 12 hours. After the reaction was completed, the temperature was lowered, the aqueous layer was separated, and the solvent in the organic layer was removed. After dissolving with chloroform, washing with water, magnesium sulfate and acid clay were added, stirred, filtered, and concentrated under reduced pressure. Thereafter, compound C1 was prepared by column chromatography using a solution in which ethyl acetate and hexane were mixed in a volume ratio of 1:50 (59 g, yield 74%).

(2) Preparation of Intermediate 2-1a

The intermediate 2-1a was prepared in the same manner as the intermediate 1-1a, except that intermediate C1 was used instead of intermediate A1 (33 g, yield 48%).

(3) Preparation of intermediate D1

The intermediate D1 was prepared in the same manner as the intermediate B1, except for using the intermediate 2-1a instead of the intermediate 1-1a (yield 87%).

Preparation Example 2-2: Synthesis of Intermediates C2 and D2

(1) Preparation of intermediate C2

Intermediates except that (2,4-dimethylbenzofuro[2,3-d]pyrimidin-8-yl)boronic acid was used instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid The intermediate C2 was prepared in the same manner as in the method of preparing C1 (54 g, 52% yield).

(2) Preparation of intermediate 2-1b

The intermediate 2-1b was prepared in the same manner as the intermediate 2-1a, except that intermediate C2 was used instead of intermediate C1 (33 g, yield 48%).

(3) Preparation of intermediate D2

The intermediate D2 was prepared in the same manner as the intermediate D1, except for using the intermediate 2-1b instead of the intermediate 2-1a (yield 80%).

Preparation Example 2-3: Synthesis of Intermediates C3 and D3

(1) Preparation of intermediate C3

Except for using (2,4-diisopropylbenzofuro[2,3-d]pyridin-8-yl)boronic acid instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid The intermediate C3 was prepared in the same manner as the intermediate C1 (42 g, yield 49%).

(2) Preparation of intermediate 2-1c

The intermediate 2-1c was prepared in the same manner as the intermediate 2-1a except for using the intermediate C3 instead of the intermediate C1 (29 g, 48% yield).

(3) Preparation of intermediate D3

The intermediate D3 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1c was used instead of the intermediate 2-1a (yield 91%).

Preparation Example 2-4: Synthesis of Intermediates C4 and D4

(1) Preparation of intermediate C4

Except for using (2,4-dihydrohexylbenzofuro[2,3-d]pyrimidin-8-yl)boronic acid instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid And the intermediate C4 was prepared in the same manner as the intermediate C1 (21 g, yield 50%).

(2) Preparation of intermediate 2-1d

The intermediate 2-1d was prepared in the same manner as the intermediate 2-1a except for using the intermediate C4 instead of the intermediate C1 (25 g, 48% yield).

(3) Preparation of intermediate D4

The intermediate D4 was prepared in the same manner as the intermediate D1, except for using the intermediate 2-1d instead of the intermediate 2-1a (yield 70%).

Preparation Example 2-5: Synthesis of Intermediates C5 and D5

(1) Preparation of intermediate C5

Intermediate C5 was prepared in the same manner as the method of preparing Intermediate C2, except that the intermediate 2-bromo-4-isopropylpyrimidine was used instead of 2-bromopyrimidine (48 g, yield 51%).

(2) Preparation of Intermediate 2-1e

The intermediate 2-1e was prepared in the same manner as the intermediate 2-1a, except that intermediate C5 was used instead of intermediate C1 (35 g, yield 41%).

(3) Preparation of intermediate D5

The intermediate D5 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1e was used instead of the intermediate 2-1a (yield 69%).

Preparation Example 2-6: Synthesis of Intermediates C6 and D6

(1) Preparation of intermediate 2-1f

6-Bromo-4-methylbenzofuro[2,3-d]pyrimidine (28 g), 4,4,5,5-tetramethyl-[1,2,3]-dioxabo in a round bottom flask Lorraine (4,4,5,5,-tetramethyl-[1,2,3]-dioxaborolane) (1.5 eq), Pd(dppf)Cl ₂ (3 mol%), potassium acetate (3 eq) Was dissolved in dioxane (300 ml) and stirred with heating at 80° C. for 12 hours. The temperature was lowered to room temperature, and the solvent was concentrated under reduced pressure. The concentrate was dissolved in chloroform (CHCl ₃ ) and washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure and precipitated in ethanol to prepare compound 2-1f. (28 g, 84% yield)

(2) Preparation of intermediate C6

Intermediate C6 was prepared in the same manner as the method of preparing Intermediate C1, except that Intermediate 2-1f was used instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (27 g, yield 70 %).

(2) Preparation of intermediate 2-1g

The intermediate 2-1g was prepared in the same manner as the intermediate 2-1a except that intermediate C6 was used instead of intermediate C1 (29 g, yield 41%).

(3) Preparation of intermediate D6

The intermediate D6 was prepared in the same manner as the intermediate D1, except that intermediate 2-1g was used instead of intermediate 2-1a (yield 72%).

Preparation Example 2-7: Synthesis of Intermediates C7 and D7

(1) Preparation of intermediate C7

Instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dimethylbenzo[4,5]thieno[2,3-d]pyrimidin-8-yl)boro The intermediate C7 was prepared in the same manner as the intermediate C1 except that nitric acid was used (54 g, yield 52%).

(2) Preparation of intermediate 2-1h

Intermediate 2-1h was prepared in the same manner as the method of preparing Intermediate 2-1a, except that Intermediate C7 was used instead of Intermediate C1 (25 g, yield 58%).

(3) Preparation of intermediate D7

The intermediate D7 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1h was used instead of the intermediate 2-1a (yield 85%).

Preparation Example 2-8: Synthesis of Intermediates C8 and D8

(1) Preparation of intermediate C8

Instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dicyclopentylbenzo[4,5]thieno[2,3-d]pyrimidin-8-yl) The intermediate C8 was prepared in the same manner as the intermediate C1 except that boronic acid was used (23 g, yield 68%).

(2) Preparation of Intermediate 2-1i

The intermediate 2-1i was prepared in the same manner as the intermediate 2-1a except for using the intermediate C8 instead of the intermediate C1 (29 g, yield 48%).

(3) Preparation of intermediate D8

The intermediate D8 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1i was used instead of the intermediate 2-1a (yield 57%).

Preparation Example 2-9: Synthesis of Intermediates C9 and D9

(1) Preparation of intermediate C9

Instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-diisopropyl-9-phenyl-9H-pyrimido[4,5-b]indol-8-yl)boro The intermediate C9 was prepared in the same manner as the intermediate C1 except that nitric acid was used (28 g, 75% yield).

(2) Preparation of intermediate 2-1j

The intermediate 2-1j was prepared in the same manner as the intermediate 2-1a, except that intermediate C9 was used instead of intermediate C1 (35 g, yield 58%).

(3) Preparation of intermediate D9

The intermediate D9 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1j was used instead of the intermediate 2-1a (yield 70%).

Preparation Example 2-10: Synthesis of Intermediates C10 and D10

(1) Preparation of intermediate C10

Same as the method of preparing Intermediate C1 except for using benzofuro[3,2-d]pyrimidin-6-ylboronic acid instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid Intermediate C10 was prepared by the method (62 g, yield 78%).

(2) Preparation of intermediate 2-1k

The intermediate 2-1k was prepared in the same manner as the intermediate 2-1a, except that intermediate C10 was used instead of intermediate C1 (58 g, yield 49%).

(3) Preparation of intermediate D10

Intermediate D10 was prepared in the same manner as the method of preparing Intermediate D1, except that Intermediate 2-1k was used instead of Intermediate 2-1a (yield 87%).

Preparation Example 2-11: Synthesis of Intermediates C11 and D11

(1) Preparation of intermediate C11

Except for using (2,4-dimethylbenzofuro[3,2-d]pyrimidin-6-yl)boronic acid instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid The intermediate C11 was prepared in the same manner as the intermediate C1 (54 g, 52% yield).

(2) Preparation of intermediate 2-1l

Intermediate 2-1l was prepared in the same manner as the method of preparing Intermediate 2-1a, except for using Intermediate C11 instead of Intermediate C1 (33 g, yield 48%).

(3) Preparation of intermediate D11

The intermediate D11 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1l was used instead of the intermediate 2-1a (yield 81%).

Preparation Example 2-12: Synthesis of Intermediates C12 and D12

(1) Preparation of intermediate C12

Intermediate C1, except that (2,4-diisopropyl[3,2-d]pyrimidin-6-yl)boronic acid was used instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid The intermediate C12 was prepared in the same manner as in the method of preparing (42 g, 49% yield).

(2) Preparation of intermediate 2-1m

The intermediate 2-1m was prepared in the same manner as the intermediate 2-1a except that intermediate C12 was used instead of intermediate C1 (29 g, yield 48%).

(3) Preparation of intermediate D12

The intermediate D12 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1m was used instead of the intermediate 2-1a (yield 90%).

Preparation Example 2-13: Synthesis of Intermediates C13 and D13

(1) Preparation of intermediate C13

Except for using (2,4-dicyclohexylbenzofuro[3,2-d]pyrimidin-8-yl)boronic acid instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid And the intermediate C13 was prepared in the same manner as the intermediate C1 (21 g, yield 50%).

(2) Preparation of intermediate 2-1n

Intermediate 2-1n was prepared in the same manner as the method of preparing Intermediate 2-1a, except that Intermediate C13 was used instead of Intermediate C1 (28 g, yield 48%).

(3) Preparation of intermediate D13

The intermediate D13 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1n was used instead of the intermediate 2-1a (yield 81%).

Preparation Example 2-14: Synthesis of Intermediates C14 and D14

(1) Preparation of intermediate C14

Instead of 2-bromopyrimidine, the intermediate 2-bromo-4-isopropylpyrimidine was substituted for benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dimethylbenzofuro Intermediate C14 was prepared in the same manner as the method of preparing Intermediate C1, except that [3,2-d]pyrimidine-6-yl)boronic acid was used (36 g, yield 51%).

(2) Preparation of Intermediate 2-1o

The intermediate 2-1o was prepared in the same manner as the intermediate 2-1a except for using the intermediate C14 instead of the intermediate C1 (35 g, yield 65%).

(3) Preparation of intermediate D14

The intermediate D14 was prepared in the same manner as the intermediate D1, except for using the intermediate 2-1o instead of the intermediate 2-1a (yield 63%).

Preparation Example 2-15: Synthesis of compounds of intermediates C15 and D15

(1) Preparation of intermediate 2-1p

Using 8-bromo-2,4-dimethylbenzofuro[3,2-d]pyrimidine instead of 6-bromo-2,4-dimethylbenzofuro[2,3-d]pyrimidine Intermediate 2-1p was prepared in the same manner as for preparing Intermediate 2-1f except (38 g, 84% yield).

(2) Preparation of intermediate C15

Intermediate C15 was prepared in the same manner as in the method of preparing Intermediate C6, except that Intermediate 2-1p was used instead of Intermediate 2-1f (42 g, 84% yield).

(2) Preparation of Intermediate 2-1q

The intermediate 2-1q was prepared in the same manner as the intermediate 2-1g except that intermediate C15 was used instead of intermediate C6 (45 g, yield 62%).

(3) Preparation of intermediate D15

Intermediate D15 was prepared in the same manner as the method of preparing Intermediate D6, except that Intermediate 2-1q was used instead of Intermediate 2-1g (yield 82%).

Preparation Example 2-16: Synthesis of Intermediates C16 and D16

(1) Preparation of intermediate C16

Instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dimethylbenzo[4,5]thieno[3,2-d]pyridin-6-yl)boronic acid The intermediate C16 was prepared in the same manner as the method of preparing the intermediate C1 except for using (54 g, 52% yield).

(2) Preparation of intermediate 2-1r

The intermediate 2-1r was prepared in the same manner as the intermediate 2-1a, except that intermediate C16 was used instead of intermediate C1 (25 g, yield 58%).

(3) Preparation of intermediate D16

The intermediate D16 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1r was used instead of the intermediate 2-1a (yield 82%).

Preparation Example 2-17: Synthesis of Intermediates C17 and D17

(1) Preparation of intermediate C17

Intermediate instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dicyclobenzo[4,5]thieno[3,2-d]pyrimidin-6-yl) The intermediate C17 was prepared in the same manner as the method of preparing the intermediate C1 except that boronic acid was used (23 g, yield 68%).

(2) Preparation of Intermediate 2-1s

The intermediate 2-1s was prepared in the same manner as the intermediate 2-1a, except that intermediate C17 was used instead of intermediate C1 (29 g, yield 48%).

(3) Preparation of intermediate D17

The intermediate D17 was prepared in the same manner as the intermediate D1, except that the intermediate 2-1s was used instead of the intermediate 2-1a (yield 57%).

Preparation Example 2-18: Synthesis of Intermediates C18 and D18

(1) Preparation of intermediate C18

Intermediate instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-diisopropyl-5-phenyl-5H-pyrimido[5,4-b]indol-6-yl) The intermediate C18 was prepared in the same manner as the method of preparing the intermediate C1 except that boronic acid was used (28 g, yield 75%).

(2) Preparation of intermediate 2-1t

The intermediate 2-1t was prepared in the same manner as the intermediate 2-1a, except that intermediate C18 was used instead of intermediate C1. 35 g, yield 58%).

(3) Preparation of intermediate D18

The intermediate D18 was prepared in the same manner as the intermediate D1, except for using the intermediate 2-1t instead of the intermediate 2-1a (yield 70%).

Preparation Example 2-17: Synthesis of Intermediates C19 and D19

(1) Preparation of intermediate C19

Instead of benzofuro[2,3-d]pyrimidin-8-ylboronic acid (2,4-dimethylbenzo[4,5]selenopheno[3,2-d]pyrimidin-6-yl)boro The intermediate C19 was prepared in the same manner as the intermediate C1 except that nitric acid was used (31 g, 82% yield).

(2) Preparation of intermediate 2-1u

The intermediate 2-1u was prepared in the same manner as the intermediate 2-1a except that intermediate C19 was used instead of intermediate C1 (44 g, yield 67%).

(3) Preparation of intermediate D19

The intermediate D19 was prepared in the same manner as the intermediate D1 except for using the intermediate 2-1u instead of the intermediate 2-1a (yield 79%).

Manufacturing Example 3

Preparation Example 3-1: Synthesis of Compound 1

In a nitrogen atmosphere, compound B1 (20 g), compound C1 (2.5 eq), methanol (methanol) 200 ml, and ethanol (ethnol) 200 ml were added and heated and stirred at a reaction temperature of 70° C. for 48 hours. After the reaction was completed, the mixture was filtered, washed with ethanol, and then subjected to column chromatography using a solution in which hexane and methanol were mixed in a volume ratio of 100:1 to prepare compound 1 (yield 35%).

MS: [M+H] ⁺ = 748.16

Preparation Example 3-2: Synthesis of Compound 2

Compound 2 was prepared in the same manner as the method of preparing compound 1, except that intermediate C2 was used instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 776.19

Preparation Example 3-3: Synthesis of Compound 3

Compound 3 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C3 was used instead of intermediate C1 (yield 55%).

MS: [M+H] ⁺ = 832.25

Preparation Example 3-4: Synthesis of Compound 4

Compound 4 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C4 was used instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 912.32

Preparation Example 3-5: Synthesis of Compound 5

Compound 5 was prepared in the same manner as the method of preparing compound 1, except that C5 was used instead of the intermediate C1 (yield 44%).

MS: [M+H] ⁺ = 818.24

Preparation Example 3-6: Synthesis of Compound 6

Compound 6 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C6 was used instead of intermediate C1 (yield 55%).

MS: [M+H] ⁺ = 756.19

Preparation Example 3-7: Synthesis of Compound 7

Compound 7 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C7 was used instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 792.17

Preparation Example 3-8: Synthesis of Compound 8

Compound 8 was prepared in the same manner as the method of preparing compound 1, except that intermediate C8 was used instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 900.26

Preparation Example 3-9: Synthesis of Compound 9

Compound 9 was prepared in the same manner as the method of preparing compound 1, except that C9 was used instead of the intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 907.3

Preparation Example 3-10: Synthesis of Compound 10

Compound 10 was prepared in the same manner as the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 (yield 42%).

MS: [M+H] ⁺ = 776.19

Preparation Example 3-11: Synthesis of Compound 11

Compound 11 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C2 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 804.32

Preparation Example 3-12: Synthesis of Compound 12

Compound 12 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C3 instead of intermediate C1 (yield 50%).

MS: [M+H] ⁺ = 860.29

Preparation Example 3-13: Synthesis of Compound 13

Compound 13 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C4 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-14: Synthesis of Compound 14

Compound 14 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and C5 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 846.27

Preparation Example 3-15: Synthesis of Compound 15

Compound 15 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B2 instead of intermediate B1 and intermediate C6 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 804.22

Preparation Example 3-16: Synthesis of Compound 16

Compound 16 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C7 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 820.2

Preparation Example 3-17: Synthesis of Compound 17

Compound 17 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C8 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 928.29

Preparation Example 3-18: Synthesis of Compound 18

Compound 18 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and C9 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 935.33

Preparation Example 3-19: Synthesis of Compound 19

Compound 19 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B3 was used instead of intermediate B1 (yield 42%).

MS: [M+H] ⁺ = 782.23

Preparation Example 3-20: Synthesis of Compound 20

Compound 20 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C2 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 810.26

Preparation Example 3-21: Synthesis of Compound 21

Compound 21 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C3 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 866.32

Preparation Example 3-22: Synthesis of Compound 22

Compound 22 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C4 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 945.39

Preparation Example 3-23: Synthesis of Compound 23

Compound 23 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and C5 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ =852.31

Preparation Example 3-24: Synthesis of Compound 24

Compound 24 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C6 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 820.26

Preparation Example 3-25: Synthesis of Compound 25

Compound 25 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C7 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 826.24

Preparation Example 3-26: Synthesis of Compound 26

Compound 26 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C8 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 934.33

Preparation Example 3-27: Synthesis of Compound 27

Compound 27 was prepared in the same manner as the method of preparing compound 1, except that intermediate B3 was used instead of intermediate B1 and C9 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 950.37

Preparation Example 3-28: Synthesis of Compound 28

Compound 28 was prepared by the same method as the method of preparing compound 1, except that intermediate B4 was used instead of intermediate B1 (yield 42%).

MS: [M+H] ⁺ = 816.3

Preparation Example 3-29: Synthesis of Compound 29

Compound 29 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C2 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 843.33

Preparation Example 3-30: Synthesis of Compound 30

Compound 30 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C3 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 900.39

Preparation Example 3-31: Synthesis of Compound 31

Compound 31 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B4 instead of intermediate B1 and intermediate C4 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 980.46

Preparation Example 3-32: Synthesis of Compound 32

Compound 32 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B4 instead of intermediate B1 and intermediate C5 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 886.38

Preparation Example 3-33: Synthesis of Compound 33

Compound 33 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C6 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 844.33

Preparation Example 3-34: Synthesis of Compound 34

Compound 34 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C7 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 886.38

Preparation Example 3-35: Synthesis of Compound 35

Compound 35 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B4 instead of intermediate B1 and intermediate C8 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 968.4

Preparation Example 3-36: Synthesis of Compound 36

Compound 36 was prepared in the same manner as the method of preparing compound 1, except that intermediate B4 was used instead of intermediate B1 and C9 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 975.44

Preparation Example 3-37: Synthesis of Compound 37

Compound 37 was prepared in the same manner as the method of preparing compound 1, except for using intermediate B5 instead of intermediate B1 (yield 42%).

MS: [M+H] ⁺ = 850.37

Preparation Example 3-38: Synthesis of Compound 38

Compound 38 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B5 instead of intermediate B1 and intermediate C2 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 878.4

Preparation Example 3-39: Synthesis of Compound 39

Compound 39 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C3 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 934.46

Preparation Example 3-40: Synthesis of Compound 40

Compound 40 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C4 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 1014.52

Preparation Example 3-41: Synthesis of Compound 41

Compound 41 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B5 instead of intermediate B1 and C5 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 920.45

Preparation Example 3-42: Synthesis of Compound 42

Compound 42 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C6 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 878.4

Preparation Example 3-43: Synthesis of Compound 43

Compound 43 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C7 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 890.38

Preparation Example 3-44: Synthesis of Compound 44

Compound 44 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C8 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 1002.47.

Preparation Example 3-45: Synthesis of Compound 45

Compound 45 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C9 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1009.51

Preparation Example 3-46: Synthesis of Compound 46

Compound 46 was prepared in the same manner as the method of preparing compound 1, except that intermediate B6 was used instead of intermediate B1 (yield 42%).

MS: [M+H] ⁺ = 912.32

Preparation Example 3-47: Synthesis of Compound 47

Compound 47 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C2 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-48: Synthesis of Compound 48

Compound 48 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C3 instead of intermediate C1 (yield 50%).

MS: [M+H] ⁺ = 996.41

Preparation Example 3-49: Synthesis of Compound 49

Compound 49 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C4 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 1076.47

Preparation Example 3-50: Synthesis of Compound 50

Compound 50 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C5 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 982.4

Preparation Example 3-51: Synthesis of Compound 51

Compound 51 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C6 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-52: Synthesis of Compound 52

Compound 52 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C7 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 956.33

Preparation Example 3-53: Synthesis of Compound 53

Compound 53 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C8 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 1064.42

Preparation Example 3-54: Synthesis of Compound 54

Compound 54 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and C9 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1071.46

Preparation Example 3-55: Synthesis of Compound 55

Compound 55 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate C10 instead of intermediate C1 (yield 42%).

MS: [M+H] ⁺ = 748.16

Preparation Example 3-56: Synthesis of Compound 56

Compound 56 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C11 was used instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 776.19

Preparation Example 3-57: Synthesis of Compound 57

Compound 57 was prepared in the same manner as the method for preparing compound 1, except that intermediate C12 was used instead of intermediate C1 (yield 50%).

MS: [M+H] ⁺ = 832.25

Preparation Example 3-58: Synthesis of Compound 58

Compound 58 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C13 was used instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 912.32

Preparation Example 3-59: Synthesis of Compound 59

Compound 59 was prepared by the same method as the method of preparing compound 1, except that C14 was used instead of the intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 818.24

Preparation Example 3-60: Synthesis of Compound 60

Compound 60 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C15 was used instead of intermediate C1 (yield 59).

MS: [M+H] ⁺ = 776.19

Preparation Example 3-61: Synthesis of Compound 61

Compound 61 was prepared in the same manner as the method of preparing compound 1, except that intermediate C16 was used instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 792.17

Preparation Example 3-62: Synthesis of Compound 62

Compound 62 was prepared in the same manner as in the method of preparing compound 1, except that intermediate C17 was used instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 900.26

Preparation Example 3-63: Synthesis of Compound 63

Compound 63 was prepared by the same method as the method of preparing compound 1, except that C18 was used instead of the intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 907.3

Preparation Example 3-64: Synthesis of Compound 64

Compound 64 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and C10 was used instead of intermediate C1 (yield 42%).

MS: [M+H] ⁺ = 776.19

Preparation Example 3-65: Synthesis of Compound 65

Compound 65 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and C11 was used instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 804.32

Preparation Example 3-66: Synthesis of Compound 66

Compound 66 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C12 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 860.29

Preparation Example 3-67: Synthesis of Compound 67

Compound 67 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B2 instead of intermediate B1 and intermediate C13 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-68: Synthesis of Compound 68

Compound 68 was prepared in the same manner as the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and C14 was used instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 846.27

Preparation Example 3-69: Synthesis of Compound 69

Compound 69 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B2 instead of intermediate B1 and intermediate C15 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 804.22

Preparation Example 3-70: Synthesis of Compound 70

Compound 70 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B2 instead of intermediate B1 and intermediate C16 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 820.2

Preparation Example 3-71: Synthesis of Compound 71

Compound 71 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and intermediate C17 was used instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 928.29

Preparation Example 3-72: Synthesis of Compound 72

Compound 72 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1 and C18 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 935.33

Preparation Example 3-73: Synthesis of Compound 73

Compound 73 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C10 instead of intermediate C1 (yield 42%).

MS: [M+H] ⁺ = 782.23

Preparation Example 3-74: Synthesis of Compound 74

Compound 74 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B3 instead of intermediate B1 and intermediate C11 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 810.26

Preparation Example 3-75: Synthesis of Compound 75

Compound 75 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C12 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 866.32

Preparation Example 3-76: Synthesis of Compound 76

Compound 76 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C13 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 946.49

Preparation Example 3-77: Synthesis of Compound 77

Compound 77 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B3 was used instead of intermediate B1 and C14 was used instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 852.31

Preparation Example 3-78: Synthesis of Compound 78

Compound 78 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C15 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 810.26

Preparation Example 3-79: Synthesis of Compound 79

Compound 79 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C16 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 826.24

Preparation Example 3-80: Synthesis of Compound 80

Compound 80 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and intermediate C17 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 933.33

Preparation Example 3-81: Synthesis of Compound 81

Compound 81 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B3 instead of intermediate B1 and C18 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 941.37

Preparation Example 3-82: Synthesis of Compound 82

Compound 82 was prepared in the same manner as the method of preparing compound 1, except that intermediate B4 instead of intermediate B1 and C10 instead of intermediate C1 were used (yield 42%).

MS: [M+H] ⁺ = 816.3

Preparation Example 3-83: Synthesis of Compound 83

Compound 83 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C11 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 844.33

Preparation Example 3-84: Synthesis of Compound 84

Compound 84 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C12 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 900.39

Preparation Example 3-85: Synthesis of Compound 85

Compound 85 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C13 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 980.46

Preparation Example 3-86: Synthesis of Compound 86

Compound 86 was prepared in the same manner as the method of preparing compound 1, except that intermediate B4 was used instead of intermediate B1 and C14 was used instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 886.38.

Preparation Example 3-87: Synthesis of Compound 87

Compound 87 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B4 instead of intermediate B1 and intermediate C15 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 844.33

Preparation Example 3-88: Synthesis of Compound 88

Compound 88 was prepared in the same manner as the method of preparing compound 1, except that intermediate B4 instead of intermediate B1 and intermediate C16 instead of intermediate C1 were used (yield 49%).

MS: [M+H] ⁺ = 860.17

Preparation Example 3-89: Synthesis of Compound 89

Compound 89 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B4 instead of intermediate B1 and intermediate C17 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 886.38

Preparation Example 3-90: Synthesis of Compound 90

Compound 90 was prepared in the same manner as the method of preparing compound 1, except that intermediate B4 was used instead of intermediate B1 and C18 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 975.44

Preparation Example 3-91: Synthesis of Compound 91

Compound 91 was prepared in the same manner as the method of preparing compound 1, except that intermediate B5 was used instead of intermediate B1, and intermediate C10 was used instead of intermediate C1 (yield 42%).

MS: [M+H] ⁺ = 850.37

Preparation Example 3-92: Synthesis of Compound 92

Compound 92 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C11 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 878.4

Preparation Example 3-93: Synthesis of Compound 93

Compound 93 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C12 instead of intermediate C2 (yield 50%).

MS: [M+H] ⁺ = 934.46

Preparation Example 3-94: Synthesis of Compound 94

Compound 94 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C13 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 1014.52

Preparation Example 3-95: Synthesis of Compound 95

Compound 95 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and C14 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 920.45

Preparation Example 3-96: Synthesis of Compound 96

Compound 96 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C15 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 878.4

Preparation Example 3-97: Synthesis of Compound 97

Compound 97 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B5 instead of intermediate B1 and intermediate C16 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 894.38

Preparation Example 3-98: Synthesis of Compound 98

Compound 98 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B5 instead of intermediate B1 and intermediate C17 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 1002.47

Preparation Example 3-99: Synthesis of Compound 99

Compound 99 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B5 instead of intermediate B1 and C18 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1009.51

Preparation Example 3-100: Synthesis of Compound 100

Compound 100 was prepared in the same manner as in the method of preparing compound 1, except that intermediate B6 was used instead of intermediate B1 and intermediate C10 was used instead of intermediate C1 (yield 42%).

MS: [M+H] ⁺ = 912.32

Preparation Example 3-101: Synthesis of Compound 101

Compound 101 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C11 instead of intermediate C1 (yield 53%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-102: Synthesis of Compound 102

Compound 102 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C12 instead of intermediate C1 (yield 50%).

MS: [M+H] ⁺ = 996.41

Preparation Example 3-103: Synthesis of Compound 103

Compound 103 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C13 instead of intermediate C1 (yield 52%).

MS: [M+H] ⁺ = 1076.47

Preparation Example 3-104: Synthesis of Compound 104

Compound 104 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and C14 instead of intermediate C1 (yield 48%).

MS: [M+H] ⁺ = 982.4

Preparation Example 3-105: Synthesis of Compound 105

Compound 105 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C15 instead of intermediate C1 (yield 59%).

MS: [M+H] ⁺ = 940.35

Preparation Example 3-106: Synthesis of Compound 106

Compound 106 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and intermediate C16 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 956.33

Preparation Example 3-107: Synthesis of Compound 107

Compound 107 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate B6 instead of intermediate B1 and intermediate C17 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 1064.42

Preparation Example 3-108: Synthesis of Compound 108

Compound 108 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate B6 instead of intermediate B1 and C18 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1071.46

Preparation Example 3-109: Synthesis of Compound 109

Compound 109 was prepared in the same manner as in the method of preparing compound 1, except that intermediate D1 was used instead of intermediate B1 and intermediate A2 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 854.18

Preparation Example 3-110: Synthesis of Compound 110

Compound 110 was prepared in the same manner as in the method of preparing compound 1, except that intermediate D2 was used instead of intermediate B1 and intermediate A3 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 913.26

Preparation Example 3-111: Synthesis of Compound 111

Compound 111 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D3 instead of intermediate B1 and intermediate A4 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1042.42

Preparation Example 3-112: Synthesis of Compound 112

Compound 112 was prepared in the same manner as in the method of preparing compound 1, except that intermediate D4 was used instead of intermediate B1 and intermediate A5 was used instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 1219.58

Preparation Example 3-113: Synthesis of Compound 113

Compound 113 was prepared in the same manner as the method of preparing compound 1, except for using intermediate D5 instead of intermediate B1 and intermediate A6 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 1062.4

Preparation Example 3-114: Synthesis of Compound 114

Compound 114 was prepared in the same manner as the method of preparing compound 1, except that intermediate D6 was used instead of intermediate B1 and intermediate A3 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 913.26

Preparation Example 3-115: Synthesis of Compound 115

Compound 115 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D7 instead of intermediate B1 and intermediate A4 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 946.27

Preparation Example 3-116: Synthesis of Compound 116

Compound 116 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D8 instead of intermediate B1 and intermediate A5 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1179.49

Preparation Example 3-117: Synthesis of Compound 117

Compound 117 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D9 instead of intermediate B1 and intermediate A6 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 116.48

Preparation Example 3-118: Synthesis of Compound 118

Compound 118 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D10 instead of intermediate B1 and intermediate A3 instead of intermediate C1 (yield 49%).

MS: [M+H] ⁺ = 871.21

Preparation Example 3-119: Synthesis of Compound 119

Compound 119 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D11 instead of intermediate B1 and intermediate A4 instead of intermediate C1 (yield 51%).

MS: [M+H] ⁺ = 930.29

Preparation Example 3-120: Synthesis of Compound 120

Compound 120 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate D12 instead of intermediate B1 and intermediate A1 instead of intermediate C1 (yield 45).

MS: [M+H] ⁺ = 1022.37

Preparation Example 3-121: Synthesis of Compound 121

Compound 121 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate D13 instead of intermediate B1 and intermediate A5 instead of intermediate C1 (yield 45).

MS: [M+H] ⁺ = 1219.58

Preparation Example 3-122: Synthesis of Compound 122

Compound 122 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D14 instead of intermediate B1 and intermediate A6 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1062.4

Preparation Example 3-123: Synthesis of Compound 123

Compound 123 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D15 instead of intermediate B1 and intermediate A5 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 913.26

Preparation Example 3-124: Synthesis of Compound 124

Compound 124 was prepared in the same manner as in the method of preparing compound 1, except for using intermediate D16 instead of intermediate B1 and intermediate A3 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 929.24

Preparation Example 3-125: Synthesis of Compound 125

Compound 125 was prepared in the same manner as in the method of preparing compound 1, except that intermediate D17 was used instead of intermediate B1 and intermediate A4 was used instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1195.47

Preparation Example 3-126: Synthesis of Compound 126

Compound 126 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D18 instead of intermediate B1 and intermediate A4 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1210.56

Preparation Example 3-127: Synthesis of Compound 127

Compound 127 was prepared in the same manner as in the method of preparing compound 1 except for using intermediate D19 instead of intermediate B1 and intermediate A4 instead of intermediate C1 (yield 45%).

MS: [M+H] ⁺ = 1058.14

Example 1

A glass substrate coated with a thin film of 1,300Å of ITO (indium tin oxide) was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

Compound HI-1 was thermally vacuum deposited to a thickness of 500Å on the ITO transparent electrode prepared as described above to form a hole injection layer.

Compound HT-1 was thermally vacuum deposited to a thickness of 800Å on the hole injection layer, and then compound HT-3 was vacuum-deposited to a thickness of 500Å to form first and second hole transport layers.

Subsequently, on the hole transport layer, the compound 21 synthesized in the preparation example as a mixture of the host H1 and H2 and a phosphorescent dopant was vacuum-deposited at 6 parts by weight based on 100 parts by weight of the total weight of the compounds H1, H2 and 21 to have a thickness of 400Å. A light emitting layer was formed.

A hole blocking layer was formed by vacuum depositing compound ET-3 on the light emitting layer to a thickness of 50Å, and an electron transport layer having a thickness of 250Å was formed by vacuum depositing compound ET-4 and LiQ on the hole blocking layer at a weight ratio of 1:1. I did. Lithium pruride (LiF) having a thickness of 10Å was sequentially deposited on the electron transport layer, and aluminum was deposited thereon to a thickness of 1000Å to form a negative electrode.

In the above process, the deposition rate of organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec. The vacuum degree was maintained between 1×10 ^-7 torr and 5×10 ^-8 torr.

Examples 2 to 20

When forming the light emitting layer, the organic light emitting device of the Example was manufactured in the same manner as in Example 1, except that the compound and parts by weight shown in Table 1 below were used instead of Compound 21 as a phosphorescent dopant.

Comparative Examples 1-1 to 1-8

The organic light emitting device of Comparative Example was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 as the phosphorescent dopant when forming the emission layer.

By applying a current to the organic light emitting device manufactured in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below.

T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance.

compound Parts by weight max
(nm) Voltage
(V
@10mA/cm ² ) efficiency
(cd/A
@10mA/cm ² ) life span
(T95, h,
@50mA/cm ² ) Example 1 21 6 523 3.45 86 210 Example 2 21 10 525 3.56 84 221 Example 3 40 6 525 3.43 84 224 Example 4 40 10 526 3.53 81 231 Example 5 45 6 524 3.42 79 208 Example 6 45 10 525 3.45 77 217 Example 7 74 6 527 3.48 83 219 Example 8 74 10 529 3.50 81 214 Example 9 88 6 528 3.42 85 208 Example 10 88 10 530 3.46 84 210 Example 11 110 6 530 3.38 88 180 Example 12 110 10 532 3.41 83 188 Example 13 120 6 529 3.42 82 219 Example 14 120 10 531 3.47 81 217 Example 15 69 6 526 3.51 82 216 Example 16 69 10 528 3.53 83 219 Example 17 122 6 530 3.48 85 221 Example 18 122 10 531 3.49 84 226 Example 19 127 6 533 3.53 80 198 Example 20 127 10 534 3.55 79 203 Comparative Example 1 T1 6 534 3.97 63 158 Comparative Example 2 T1 10 535 4.01 60 164 Comparative Example 3 T2 6 532 4.03 59 161 Comparative Example 4 T2 10 533 4.07 58 170 Comparative Example 5 T3 6 532 3.92 62 159 Comparative Example 6 T3 10 532 3.98 61 160 Comparative Example 7 T4 6 528 4.18 63 165 Comparative Example 8 T4 10 529 4.20 61 177

According to Table 1, the device using the compound represented by Formula 1 of the present application exhibits low driving voltage, high efficiency, and high lifespan characteristics compared to devices using the T1 to T4 compound having 0 or 1 N of X1 to X4. I can confirm.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer
9: hole blocking layer

Claims (12)

Organometallic compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
X is NR, O, S or Se,
X1 is N or CRa, X2 is N or CRb, X3 is N or CRc, X4 is N or CRd, and at least two of X1 to X4 are N,
R is an aryl group,
Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group unsubstituted or substituted with deuterium; A cycloalkyl group unsubstituted or substituted with deuterium; Or an aryl group,
R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A silyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms; An alkyl group unsubstituted or substituted with deuterium; Or a cycloalkyl group,
n is 1 or 2,
a1 is an integer of 0 to 4, and if a1 is 2 or more, R1 is the same as or different from each other,
a2 is an integer of 0 to 2, and if a2 is 2, R2 is the same as or different from each other,
a3 is an integer from 0 to 4, and if a3 is 2 or more, R3 is the same as or different from each other,
a4 is an integer of 0 to 4, and when a4 is 2 or more, R4 is the same as or different from each other. The organometallic compound of claim 1, wherein the formula 1 is represented by any one of the following formulas 2-A to 2-F:
[Formula 2-A]

[Formula 2-B]

[Formula 2-C]

[Formula 2-D]

[Formula 2-E]

[Formula 2-F]

In the formulas 2-A to 2-F,
The definitions of X, X1 to X4, R1 to R4, a1 to a4, and n are as defined in Formula 1. The organometallic compound of claim 1, wherein the formula 1 is represented by the following formula 3-A:
[Formula 3-A]

In Formula 3-A,
The definitions of X, Ra, Rc, R1 to R4, a1 to a4, and n are as defined in Formula 1. The organometallic compound of claim 1, wherein the formula 1 is represented by the following formula 3-B:
[Formula 3-B]

In Formula 3-B,
The definitions of X, Rb, Rd, R1 to R4, a1 to a4, and n are as defined in Formula 1. The method according to claim 1,
R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A methyl group unsubstituted or substituted with deuterium; Isopropyl group; Cyclohexyl group; Or an organometallic compound which is a silyl group substituted with a methyl group. The organometallic compound of claim 1, wherein the organometallic compound represented by Formula 1 is any one selected from the following compounds:

. An organic light-emitting device comprising a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein the organometallic compound according to any one of claims 1 to 6 is An organic light-emitting device that is included in an organic material layer provided between the first electrode and the second electrode. The method of claim 7, wherein the organic material layer includes at least one of an electron injection layer, an electron transport layer, and a layer for simultaneously injecting and transporting electrons, and the organometallic compound simultaneously performs the electron injection layer, an electron transport layer, and electron injection and transport. The organic light emitting device is included in at least one of the layers. The organic light-emitting device of claim 7, wherein the organic material layer includes an emission layer, and the organic metal compound is included in the emission layer. The organic light-emitting device of claim 9, wherein the emission layer is a green emission layer. The organic light-emitting device of claim 9, wherein the organometallic compound is included as a dopant in the light-emitting layer. The method according to claim 7, wherein the organic material layer comprises at least one layer of a hole injection layer, a hole transport layer, and a layer that simultaneously transports and injects holes, and the organometallic compound performs the hole injection layer, the hole transport layer, and the hole transport and injection. An organic light emitting device that is included in at least one of the simultaneous layers.

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