KR20200037542A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides: a novel mixture capable of improving luminous efficiency, stability, and lifespan of an element; an organic electronic element which uses the same; and an electronic device thereof. By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electronic element, and also significantly improve a lifespan of the element.

Description

Compound for organic electric element, organic electric element using the same, and its electronic device {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on the function.

In the case of a bis-type cyclic compound containing a hetero atom, a difference in properties according to a material structure is very large, and thus, it is applied to various layers as a material for an organic electric device. In particular, the band gap (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. have different characteristics depending on the number of rings, fused positions, and the type and arrangement of heteroatoms. This has been going on.

In a phosphorescent organic electrical device using a phosphorescent dopant material, the LUMO and HOMO levels of the host material are factors that greatly affect the efficiency and lifetime of the organic electrical device. Accordingly, it is possible to control the charge balance in the light-emitting layer, quenching the dopant, and prevent the decrease in efficiency and the life due to light emission at the hole transport layer interface.

In the case of host materials for fluorescence and phosphorescence emission, recently, the efficiency and lifespan of organic electric devices using TADF (Thermal activatied delayed fluorescent), Exciplex, etc., are being studied. In particular, the method of energy transfer from host materials to dopant materials has been investigated. There is a lot of research going on.

Although there are several methods for identifying energy transfer in a light emitting layer for TADF (Thermal Activated Delayed Fluorescent), exciplex, it can be easily confirmed by PL lifetime (TRTP) measurement.

The TRTP (Time resolved transient PL) measurement method is a method of observing the decay time of the spectrum over time after irradiating a pulsed light source to the host thin film. It is a measurement method. The TRTP measurement is a measurement method capable of distinguishing between fluorescence and phosphorescence, energy transfer method in mixed host material, exciplex energy transfer method, and TADF energy transfer method.

As described above, there are various factors affecting efficiency and lifespan depending on the manner in which energy is transferred from the host material to the dopant material, and the energy transmission method is different according to the material, so that the development of a stable and efficient host material for an organic electric device This is not done enough. Therefore, the development of new materials continues to be required, and in particular, the development of the host material of the light emitting layer is urgently required.

KR 101170666 B1

The present invention has been proposed to solve the problems of the phosphorescent host material as described above, the charge balance in the light emitting layer by adjusting the HOMO level for the host material of the phosphorescent dopant-containing organic electroluminescent device containing a phosphorescent dopant and the efficiency, life span It is an object of the present invention to provide an organic electrical device using the compound and an electronic device thereof.

The present invention is to reduce the energy barrier between the light emitting layer and the adjacent layer by containing a specific first host material in combination with a specific first host material as a main component in order to control efficient hole injection in the light emitting layer of the phosphorescent organic electroluminescent device. It is possible to maximize the charge balance in the light emitting layer to provide high efficiency and high lifespan of the organic electric device.

The present invention relates to an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer. It provides an organic electric device comprising a first host compound represented by (1) and a second host compound represented by the formula (2).

 Formula (1) Formula (2)

In addition, the present invention provides an organic electric device using the compound represented by the above formulas and an electronic device thereof.

By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electric device, and also significantly improve the life of the device.

1 is an exemplary view of an organic electroluminescent device according to the present invention.

Hereinafter, with reference to the embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that detailed descriptions of related known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise stated, the meaning of the following terms is as follows:

The terms "halo" or "halogen" as used herein are fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise noted.

The term "alkyl" or "alkyl group" used in the present invention has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycle. By radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise specified.

The term "heteroalkyl group" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The terms "alkenyl group", "alkenyl group" or "alkynyl group" as used in the present invention have a double or triple bond of 2 to 60 carbon atoms, unless otherwise specified, and include straight or branched chain groups. , But is not limited to this.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

The term "alkoxyl group", "alkoxy group", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has a carbon number of 6 to 60 unless otherwise specified, and is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multi-ring aromatic, and includes an aromatic ring formed by adjacent substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, dimethylfluorene group, diphenylfluorene group, or spirofluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has a carbon number described herein.

Also, when the prefix is named in succession, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is not limited thereto. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

The term “heteroatom” as used herein refers to N, O, S, P or Si, unless otherwise stated.

In addition, "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming a ring. For example, "heterocyclic group" includes the following compounds.

Unless otherwise specified, the term "aliphatic" as used herein refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" used in the present invention refers to an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, It contains a saturated or unsaturated ring.

Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR ', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms. Is a cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" used in the present invention is represented by -RO-R ', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 30 carbon atoms. It is an aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

In addition, unless otherwise specified, the formula used in the present invention is applied in the same manner as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ means non-existent, that is, when a is 0, it means that hydrogen is bonded to all of the carbons forming the benzene ring. The formula or compound may be omitted. When a is an integer of 1, one substituent R ¹ is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, each of them is bonded as follows, where R ¹ may be the same or different from each other. When a is an integer of 4 to 6, it binds to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bound to the carbon forming the benzene ring is omitted.

Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.

The present invention relates to an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer. It provides an organic electric device comprising a first host compound represented by (1) and a second host compound represented by the formula (2).

Formula (1) Formula (2)

        {In the formulas (1) and (2) above,

1) X and Y are each independently O; S; CR'R "; SiR'R" or Se ;,

2) a and b are each independently 0 or 1, provided that a + b is 1 or more,

3) R 'and R "are each independently hydrogen; an alkyl group of C ₁ to C ₅₀ ; an aryl group of C ₆ to C ₆₀ ; and a heteroaryl group of C ₂ to C ₆₀ ; or R' And R "form a ring with each other to form a spiro ring,

4) L ¹ , L ² and L 'are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Or a C ₂ ~ C ₆₀ heteroarylene group; and

5) Ar ¹ and Ar ² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-NR'R ";

6) Z is NR ', O, S, CR'R ", SiR'R", or Se,

7) R ¹ to R ⁶ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,

R _a and R _b are independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom; is selected from the group consisting of,

When l, m, n, o, p, and q are 2 or more, they are the same as or different from each other, and a plurality of R ¹ , a plurality of R ² , a plurality of R ³ , a plurality of R ⁴ , and a plurality of R ^{5 to} each other, a plurality of R ^{6 to} each other can be combined to form an aromatic and heteroaromatic ring,

8) The A and B rings are each independently an aryl group of C ₆ to C ₆₀ or a heteroaryl group of C ₂ to C ₆₀ , and one of A and B is an aryl group of C ₁₀ to C ₆₀ ,

9) n, l, p and q are any integers from 0 to 4, m is 0 or 1, o is any integer from 0 to 3,

10) One of X ¹ and X ² is N and the other is C-Ar ² ,

Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio; Alkoxyl group of C ₁ -C ₂₀ ; C ₁ -C ₂₀ alkyl group; Alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ Aryl group; A C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group and C ₈ -C ₂₀ arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, also, these substituents may combine with each other to form a ring, wherein ''Cycle' means a C ₃ -C ₆₀ aliphatic ring or a C ₆ -C ₆₀ aromatic ring or a C ₂ -C ₆₀ heterocycle or a combination thereof, and includes a saturated or unsaturated ring.}

The compound represented by the formula (1) in the present invention provides an organic electric device comprising a compound represented by the following formula (3) or (4).

         Formula (3) Formula (4)

(In the formulas (3) and (4), X, Y, Z, Ar ¹ , L ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , l, m, n, o, and p are Same as defined above)

As another specific example, the present invention provides an organic electric device in which the compound represented by the formula (1) includes a compound represented by any one of the following formulas (5) to (12).

    Formula (5) Formula (6) Formula (7) Formula (8)

  Formula (9) Formula (10) Formula (11) Formula (12)

(In the formulas (5) to (12), X, Y, Z, Ar ¹ , L ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , l, m, n, o, and p are Same as defined above)

In addition, the present invention provides an organic electric device including a compound in which all of l, m, n, o and p are 0 in the formula (1).

As another example, the present invention in the formula (1), any one of the R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an organic electric device comprising a compound in which a pair of neighboring pairs to each other to form a ring Provides

In addition, the present invention in the formula (1), the X or Y provides an organic electric device comprising a compound of S or O.

As a specific example, the formula (1) in the present invention includes the following compound.

On the other hand, the present invention provides an organic electric device in which the compound represented by the formula (2) includes a compound represented by the following formula (13) or (14).

              Formula (13) Formula (14)

(In the above formulas (13) and (14), A, B, L ² , Ar ² , R ⁶ and q are the same as defined above.)

The present invention provides an organic electric device comprising a compound represented by any one of the following (A-1) to (A-9) of the A and B rings of the compound represented by the formula (2).

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)

(A-8) (A-9)

(In the formulas (A-1) to (A-9), R ¹⁰ is the same as R ¹ above,

* Indicates the bonding position of the A and B rings.)

As another example, the present invention includes compounds represented by any one of the following formulas (15) to (28).

    Formula (15) Formula (16) Formula (17)

    Formula (18) Formula (19) Formula (20)

Formula (21) Formula (22) Formula (23)

Formula (24) Formula (25) Formula (26)

Formula (27) Formula (28)

(In the formulas (15) to (28),

L ² , X ¹ , X ² , R ⁶ and q are the same as defined above,

R ¹² and R ¹³ are the same as R ¹ defined above,

s and u are each independently an integer from 0 to 6,

t is an integer from 0 to 4,

v and w are each independently an integer of 0 to 8.)

In addition, the present invention provides an organic electric device comprising a compound in which R ⁶ of the compound represented by the formula (2) is hydrogen.

As a specific example, the formula (2) in the present invention includes the following compound.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 120 and a second electrode formed on the substrate 110. Between (180) it is provided with an organic layer containing the compound represented by the formula (1) and (2). At this time, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer sequentially comprises a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, a light emitting auxiliary layer 151, an electron transport layer 160 and an electron injection layer 170 on the first electrode 120. It can contain. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like may be further included, and the electron transport layer 160, etc. may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode. The compound containing Formula 1 of the present invention may be used as a material for the light efficiency improving layer or the protective layer.

On the other hand, even in the same core, the band gap, electrical properties, and interfacial properties may vary depending on which substituents are attached to which positions, so the selection of the core and the combination of sub-substituents coupled thereto are also very good. It is important, especially when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer 160 are formed thereon. After forming an organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and the electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.

Accordingly, the present invention provides a compound represented by the formula (1) and the formula (2) in an ratio of any one of 1: 9 to 9: 1 to provide an organic electric device included in the light emitting layer, preferably Is 1: 9 to 5: 5, more preferably mixed in a ratio of 2: 8 to 3: 7 and included in the light emitting layer.

The present invention further comprises a light efficiency improving layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer from one side of the first electrode in the organic electric device. An organic electric device is provided.

In addition, in the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, and the organic material layer according to the present invention can be formed by various methods Therefore, the scope of the present invention is not limited by the forming method.

The organic electric device according to an embodiment of the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, the R (Red), G (Green), B (Blue) light emitting units are arranged in a mutually planar side-by-side manner, and the stacking method in which the R, G, and B light-emitting layers are stacked up and down. There is, there is a color conversion material (CCM) method using electroluminescence of the blue (B) organic light-emitting layer and photo-luminescence of the inorganic phosphor using light therefrom, the present invention Can be applied to such WOLED.

In addition, the present invention is a display device comprising the above-described organic electric element; And a control unit for driving the display device.

In another aspect, the present invention provides an electronic device characterized in that the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

Hereinafter, examples of the synthesis of the compounds represented by the formulas (1) and (2) of the present invention and the production examples of the organic electroluminescent device of the present invention will be specifically described with reference to the following examples of the present invention. It is not limited.

[Synthesis Example 1]

The compound represented by Chemical Formula (1) according to the present invention (final product 1) is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Scheme 1>

1. Synthesis Example of Sub 1

Sub 1 of Scheme 1 may be synthesized by the following Reaction Scheme 2, but is not limited thereto.

<Reaction Scheme 2> (X '= I, Br, Cl)

Synthesis examples of compounds belonging to Sub 1 of Scheme 2 are as follows.

1. Synthesis Example of Sub 1-1 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-I-1

2-Chloroaniline (67.2g, 525mmol), 1,4-Dibromodibenzothiophene (150g, 438mmol), Pd ₂ (dba) ₃ (16.2g, 17.4mmol), P (t-Bu) ₃ (15g, 43.8) in a round bottom flask mmol), NaO (t-Bu) (126g, 1317mmol) and Toluene (1.5L) are added. Then, heating was refluxed for 4 hours at 70 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 1-I-1 (135 g, 79%).

Synthesis of Sub 1-II-1

To the round bottom flask, add Sub 1-I-1 (135g, 348mmol), PPh ₃ (228g, 867mmol), and o- Dichlorobenzene (900mL). Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 1-II-1 (91.8g, 75%).

Synthesis of Sub 1-1

Round bottom flask with Sub 1-II-1 (30.6g 87mmol), 1-Bromonaphthalene (21.5g, 104mmol), Pd ₂ (dba) ₃ (3.2g, 3.5mmol), P (t-Bu) ₃ (1.8g , 8.7mmol), NaO (t-Bu) (25g, 261mmol), Toluene (300mL). Then, it was heated to reflux for 8 hours at 110 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 1-1 (31.6 g, 74%).

2. Synthesis Example of Sub 1-2 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-2

Round bottom flask Sub 1-II-1 (30g, 84mmol), Iodobenzene (20.7g, 102mmol), Pd ₂ (dba) ₃ (3g, 3.3mmol), P (t-Bu) ₃ (1.8g, 8.4mmol) ), NaO (t-Bu) (24.6g, 255mmol), Toluene (240mL) was used to obtain the product Sub 1-2 (28g, 76%) using the synthesis method of Sub 1-1.

Synthesis Example of Sub 1-3 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-3

Round bottom flask with Sub 1-II-1 (30.6g 87mmol), 4-Iodo-1,1'-biphenyl (29.2g, 104mmol), Pd ₂ (dba) ₃ (3.2g, 3.5mmol), P (t -Bu) ₃ (1.8g, 8.7mmol), NaO (t-Bu) (25g, 261mmol), Toluene (300mL) using the synthesis method of Sub 1-1, the product Sub 1-3 (32g, 74% ).

Synthesis Example of Sub 1-5 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-5

Round bottom flask Sub 1-II-1 (30.6g 87mmol), 2-Bromonaphthalene (21.5g, 104mmol), Pd ₂ (dba) ₃ (3.2g, 3.5mmol), P (t-Bu) ₃ (1.8g , 8.7mmol), NaO (t-Bu) (25g, 261mmol), and Toluene (300mL) were obtained using the synthesis method of Sub 1-1 to obtain the product Sub 1-5 (29.1g, 70%).

Synthesis Example of Sub 1-6 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-I-6 (when a = 1, b = 0, X = S)

2-Chloroaniline (22.4g, 175mmol), 2,4-Dibromodibenzothiophene (50g, 146mmol), Pd ₂ (dba) ₃ (5.4g, 5.8mmol), P (t-Bu) ₃ (5g, 14.6) mmol), NaO (t-Bu) (42 g, 439 mmol), and Toluene (500 mL) were obtained using the synthesis method of Sub 1-I-1 to obtain the product Sub 1-I-6 (46 g, 90%).

Synthesis of Sub 1-II-6

Sub 1-II-6 (45g, 116mmol), PPh ₃ (76g, 289mmol), and o- Dichlorobenzene (300mL) were added to the round bottom flask using the synthesis method of Sub 1-II-1. 6 (32.6 g, 80%).

Synthesis of Sub 1-6

Round bottom flask Sub 1-II-6 (10g, 28mmol), Iodobenzene (6.9g, 34mmol), Pd ₂ (dba) ₃ (1g, 1.1mmol), P (t-Bu) ₃ (0.6g, 2.8mmol ), NaO (t-Bu) (8.2 g, 85 mmol), Toluene (80 mL) was obtained using the synthesis method of Sub 1-1 to obtain the product Sub 1-6 (10 g, 84%).

Synthesis example of Sub 1-7 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-7

Round bottom flask Sub 1-II-6 (10g, 28mmol), 4-Iodo-1,1'-biphenyl (9.5g, 34mmol), Pd ₂ (dba) ₃ (1g, 1.1mmol), P (t- Bu) ₃ (0.6g, 2.8mmol), NaO (t-Bu) (8.2g, 85mmol), Toluene (80mL) using the synthesis method of Sub 1-1 above Sub 1-7 (10g, 71%) ).

Synthesis example of Sub 1-14 (when a = 1, b = 0, X = S)

Synthesis of Sub 1-I-14

2-Chloronaphthalen-1-amine (31g, 175mmol), 2,4-Dibromodibenzothiophene (50g, 146mmol), Pd ₂ (dba) ₃ (5.4g, 5.8mmol), P (t-Bu) ₃ ( 5g, 14.6mmol), NaO (t-Bu) (42g, 439mmol), Toluene (500mL) was used to synthesize the product Sub 1-I-14 (48g, 75%) using the synthesis method of Sub 1-I-1. Got.

Synthesis of Sub 1-II-14

In a round bottom flask, add Sub 1-I-14 (30 g, 68 mmol), PPh ₃ (45 g, 171 mmol), and o- Dichlorobenzene (150 mL). Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 1-II-14 (25g, 93%).

Synthesis of Sub 1-14

Round bottom flask Sub 1-II-14 (25g, 62mmol), Iodobenzene (15g 75mmo), Pd ₂ (dba) ₃ (2.g, 2.5mmol), P (t-Bu) ₃ (1.3g (6.2mmol) ), NaO (t-Bu) (18g, 186mmol), Toluene (300mL) is added and then heated to reflux for 8 hours at 110 ° C. When the reaction is complete, distilled water is added at room temperature and diluted with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 1-14 (20 g, 67%).

Synthesis example of Sub 1-29 (when a = 1, b = 0, X = C)

Synthesis of Sub 1-I-29

2-Chloronaphthalen-1-amine (31g, 175mmol), 1,4-dibromo-9,9-dimethyl-9H-fluorene (51g, 146mmol), Pd ₂ (dba) ₃ (5.4g, 5.8mmol) in round bottom flask ), P (t-Bu) ₃ (5g, 14.6mmol), NaO (t-Bu) (42g, 439mmol), Toluene (500mL) using the synthesis method of Sub 1-I-1, product Sub 1- I-29 (36 g, 63%) was obtained.

Synthesis of Sub 1-II-29

To the round bottom flask, Sub 1-I-29 (27 g, 68 mmol), PPh ₃ (45 g, 171 mmol), o -Dichlorobenzene (150 mL) was synthesized using the synthesis method of Sub 1-II-1. 29 (22g, 92%).

Synthesis of Sub 1-29

Round bottom flask Sub 1-II-29 (22g, 62mmol), 2-Bromonaphthalene (15g 74mmo), Pd ₂ (dba) ₃ (2.g, 2.5mmol), P (t-Bu) ₃ (1.3g ( 6.2mmol), NaO (t-Bu) (18g, 186mmol), and Toluene (300mL) were obtained using the synthesis method of Sub 1-1 to obtain the product Sub 1-29 (20g, 67%).

Synthesis example of Sub 1-25 (when a = 1, b = 0, X = O)

Synthesis of Sub 1-I-25

2-Chloronaphthalen-1-amine (23.45 g, 183.85 mmol), 1,4-dibromodibenzo [b, d] furan (50 g, 153.4 mmol), Pd ₂ (dba) ₃ (5.58 g, 6.1 mmol) in a round bottom flask ), P (t-Bu) ₃ (3.1 g, 15.34 mmol), NaO (t-Bu) (44.32 g, 461.2 mmol), Toluene (340 mL) using the synthesis method of Sub 1-I-1 Product Sub 1-I-25 (41.7 g, 73%) was obtained.

Synthesis of Sub 1-II-25

To the round bottom flask, Sub 1-I-25 (47 g, 126.1 mmol), PPh ₃ (82.7 g, 315.3 mmol), and o- Dichlorobenzene (505 mL) were prepared using the synthesis method of Sub 1-II-1. Sub 1-II-25 (35.62 g, 84%) was obtained.

Synthesis of Sub 1-25

In a round bottom flask, Sub 1-II-25 (47 g, 126.13 mmol), Bromobenzene (19.59 g 124.79 mmol), Pd ₂ (dba) ₃ (3.79 g, 4.14 mmol), P (t-Bu) ₃ (2.11 g) , 10.4 mmol), NaO (t-Bu) (30.08 g, 313.045 mmol), Toluene (230 mL) using the synthesis method of Sub 1-1 to obtain the product Sub 1-25 (34.77 g, 82%) .

Sub 1 example

Meanwhile, the compound belonging to Sub 1 may be the following compound, but is not limited thereto, and Table 1 shows the FD-MS value of the compound belonging to Sub 1.

 compound FD-MS compound FD-MS Sub 1-1 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 1-2 m / z = 427.00 (C24HBrNS = 428.34) Sub 1-3 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 1-4 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 1-5 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 1-6 m / z = 427.00 (C24HBrNS = 428.34) Sub 1-7 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 1-8 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 1-9 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 1-10 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 1-11 m / z = 605.06 (C ₃₆ H ₂₀ BrN ₃ S = 606.53) Sub 1-12 m / z = 555.04 (C ₃₂ H ₁₈ BrN ₃ S = 556.47) Sub 1-13 m / z = 603.07 (C ₃₈ H ₂₂ BrNS = 604.56) Sub 1-14 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 1-15 m / z = 527.03 (C ₃₂ H ₁₈ BrNS = 528.46) Sub 1-16 m / z = 629.08 (C ₄₀ H ₂₄ BrNS = 630.59) Sub 1-17 m / z = 554.05C ₃₃ H ₁₉ BrN ₂ S = 555.49) Sub 1-18 m / z = 734.11 (C ₄₅ H ₂₇ BrN ₄ S = 735.69) Sub 1-19 m / z = 721.08 (C ₄₄ H ₂₄ BrN ₃ OS = 722.65) Sub 1-20 m / z = 629.08 (C ₄₀ H ₂₄ BrNS = 630.59) Sub 1-21 m / z = 529.02 (C ₃₀ H ₁₆ BrN ₃ S = 530.44) Sub 1-22 m / z = 555.04 (C ₃₂ H ₁₈ BrN ₃ S = 556.47) Sub 1-23 m / z = 581.06 (C ₃₄ H ₂₀ BrN ₃ S = 582.51) Sub 1-24 m / z = 600.06 (C ₃₃ H ₂₁ BrN ₄ OS = 601.52) Sub 1-25 m / z = 411.03 (C ₂₄ H ₁₄ BrNO = 412.28) Sub 1-26 m / z = 671.07 (C ₄₀ H ₂₂ BrN ₃ OS = 672.59) Sub 1-27 m / z = 593.04 (C ₃₆ H ₂₀ BrNOS = 594.52) Sub 1-28 m / z = 437.08 (C ₂₇ H ₂₀ BrN = 438.36) Sub 1-29 m / z = 487.09 (C ₃₁ H ₂₂ BrN = 488.42) Sub 1-30 m / z = 453.05 (C ₂₆ H ₂₀ BrNSi = 454.43) Sub 1-31 m / z = 474.95 (C ₂₄ H ₁₄ BrNSe = 475.24)

2. Synthesis Example of Sub 2

Sub 2 of Scheme 1 may be synthesized by the following Reaction Scheme 3, but is not limited thereto.

<Scheme 3> (X '= I, Br, Cl)

Synthesis examples of compounds belonging to Sub 2 of Scheme 3 are as follows.

Synthesis example of Sub 2-1 (when a = 0, b = 1, Y = S)

Synthesis of Sub 2-I-1

2-Bromodibenzothiophene (100g, 380mmol), 2-Nitrophenyl boronic acid (76g, 456mmol), Pd (PPh ₃ ) ₄ (18g, 15mmol), NaOH (46g, 1140mmol), THF (1.2L) / H _{Add 2} O (0.6L). Then, heating was refluxed for 4 hours at 70 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 2-I-1 (99 g, 85%).

Synthesis of Sub 2-II-1

To the round bottom flask, add Sub 2-I-1 (99g, 323mmol), PPh ₃ (218g, 808mmol), and o -Dichlorobenzene (1.0L). Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 2-II-1 (70 g, 80%).

Synthesis of Sub 2-III-1

To the round bottom flask, add Sub 2-II-1 (70g, 293mmol), N-Bromosuccinimide (52g, 293mmol), and Methylene chloride (1L). Then, the mixture was stirred at room temperature for 4 hours. After the reaction is completed, distilled water is added and then extracted with Methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 2-III-1 (86 g, 83%).

Synthesis of Sub 2-1

Round bottom flask Sub 2-III-1 (30g, 84mmol), Iodobenzene (20.7g, 102mmol), Pd ₂ (dba) ₃ (3g, 3.3mmol), P (t-Bu) ₃ (1.8g, 8.4mmol) ), NaO (t-Bu) (24.6g, 255mmol), Toluene (240mL) is added. Then, it was heated to reflux for 8 hours at 110 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 2-1 (28 g, 76%).

Synthesis Example of Sub 2-2 (a = 0, b = 1, Y = S)

Synthesis of Sub 2-2

Round bottom flask Sub 2-III-1 (30g, 84mmol), 4-Iodo-1,1'-biphenyl (28.6g, 102mmol), Pd ₂ (dba) ₃ (3g, 3.3mmol), P (t- Bu) ₃ (1.8g, 8.4mmol), NaO (t-Bu) (24.6g, 255mmol), Toluene (240mL) using the synthesis method of Sub 2-1 above Sub 2-2 (32g, 76%) ).

Synthesis of Sub 2-3 (when a = 0, b = 1, Y = S)

Synthesis of Sub 2-3

Round bottom flask Sub 2-III-1 (30g, 84mmol), 3-Bromo-1,1'-biphenyl (23.8g, 102mmol), Pd ₂ (dba) ₃ (3g, 3.3mmol), P (t- Bu) ₃ (1.8g, 8.4mmol), NaO (t-Bu) (24.6g, 255mmol), Toluene (240mL) using the synthesis method of Sub 2-1, the product Sub 2-3 (34g, 80%) ).

Synthesis Example of Sub 2-37 (a = 0, b = 1, Y = O)

Synthesis of Sub 2-I-37

2-Bromodibenzofuran (50g, 202mmol), 2-Nitrophenyl boronic acid (40.5g, 242mmol), Pd (PPh ₃ ) ₄ (9.3g, 8mmol), NaOH (24g, 606mmol), THF (600mL) / The product Sub 2-I-37 (43 g, 74%) was obtained using H ₂ O (300 mL) using the synthesis method of Sub 2-I-1.

Synthesis of Sub 2-II-37

Sub 2-I-37 (43g, 110mmol), PPh ₃ (72g, 276mmol), and o- Dichlorobenzene (350mL) were added to the round bottom flask using the synthesis method of Sub 2-II-1. 37 (23g, 82%).

Synthesis of Sub 2-III-37

To the round bottom flask, Sub 2-II-37 (23g, 89mmol), N-Bromosuccinimide (16g, 89mmol), and Methylene chloride (300mL) were synthesized using the synthesis method of Sub 2-III-1. 37 (21 g, 70%).

Synthesis of Sub 2-37

Round bottom flask Sub 2-III-37 (21g, 62mmol), Iodobenzene (15.3g, 75mmol), Pd ₂ (dba) ₃ (2.3g, 2.5mmol), P (t-Bu) ₃ (1.3g, 6.2 mmol), NaO (t-Bu) (18 g, 187 mmol), and Toluene (200 mL) were obtained using the synthesis method of Sub 2-1 to obtain Sub 2-37 (16 g, 63%).

Synthesis Example of Sub 2-144 (a = 0, b = 1, Y = C)

Synthesis of Sub 2-I-144

3-bromo-9,9-dimethyl-9H-fluorene (50g, 183.04 mmol), 2-Nitrophenyl boronic acid (36.6 g, 219.28 mmol), Pd (PPh ₃ ) ₄ (8.4 g, 7.25 mmol) in a round bottom flask , NaOH (22 g, 549.11 mmol), THF (805 mL) / H ₂ O (402 mL) using the above Sub 2-I-1 synthesis method Product Sub 2-I-144 (47.72 g, 69%) Got

Synthesis of Sub 2-II-144

To the round bottom flask, Sub 2-I-144 (47 g, 149 mmol), PPh ₃ (97.7 g, 372.48 mmol), and o- Dichlorobenzene (596 mL) were prepared using the synthesis method of Sub 2-II-1. Sub 2-II-144 (30.41 g, 72%) was obtained.

Synthesis of Sub 2-III-144

To the round bottom flask, Sub 2-II-144 (30g, 89mmol), N-Bromosuccinimide (18.8 g, 105.9 mmol), Methylene chloride (318 mL) was synthesized using the synthesis method of Sub 2-III-1. -III-144 (18.24 g, 53%).

Synthesis of Sub 2-144

In a round bottom flask, Sub 2-III-144 (18 g, 49.7 mmol), Iodobenzene (12.26 g, 60.1 mmol), Pd ₂ (dba) ₃ (1.83 g, 2 mmol), P (t-Bu) ₃ (1.01 g, 4.97 mmol), NaO (t-Bu) (14.4 g, 149.9 mmol), Toluene (109 mL) using the synthesis method of Sub 2-1 above to give the product Sub 2-144 (15.03 g, 69%). Got.

Sub 2 example

Meanwhile, the compound belonging to Sub 2 may be the following compound, but is not limited thereto, and Table 2 shows the FD-MS value of the compound belonging to Sub 2.

compound FD-MS compound FD-MS Sub 2-1 m / z = 427.00 (C24HBrNS = 428.34) Sub 2-2 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-3 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-4 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 2-5 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 2-6 m / z = 483.07 (C ₂₈ H ₂₂ BrNS = 484.45) Sub 2-7 m / z = 507.03 (C ₂₉ H ₁₈ BrNOS = 508.43) Sub 2-8 m / z = 467.03 (C ₂₇ H ₁₈ BrNS = 468.41) Sub 2-9 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-10 m / z = 427.00 (C24HBrNS = 428.34) Sub 2-11 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-12 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-13 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 2-14 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 2-15 m / z = 582.05 (C ₃₃ H ₁₉ BrN ₄ S = 583.50) Sub 2-16 m / z = 581.06 (C ₃₄ H ₂₀ BrN ₃ S = 582.51) Sub 2-17 m / z = 581.06 (C ₃₄ H ₂₀ BrN ₃ S = 582.51) Sub 2-18 m / z = 581.06 (C ₃₄ H ₂₀ BrN ₃ S = 582.51) Sub 2-19 m / z = 555.04 (C ₃₂ H ₁₈ BrN ₃ S = 556.47) Sub 2-20 m / z = 611.01 (C ₃₄ H ₁₈ BrN ₃ S ₂ = 612.56) Sub 2-21 m / z = 681.09 (C ₄₂ H ₂₄ BrN ₃ S = 682.63) Sub 2-22 m / z = 542.05 (C ₃₂ H ₁₉ BrN ₂ S = 543.48) Sub 2-23 m / z = 665.08 (C ₄₃ H ₂₄ BrNS = 666.63) Sub 2-24 m / z = 599.11 (C ₃₆ H ₁₈ D ₅ BrN ₂ S = 600.58) Sub 2-25 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-26 m / z = 502.01 (C ₂₉ H ₁₅ BrN ₂ S = 503.41) Sub 2-27 m / z = 629.08 (C ₄₀ H ₂₄ BrNS = 630.59) Sub 2-28 m / z = 605.06 (C ₃₆ H ₂₀ BrN ₃ S = 606.53) Sub 2-29 m / z = 657.09 (C ₄₀ H ₂₄ BrN ₃ S = 658.61) Sub 2-30 m / z = 631.07 (C ₃₈ H ₂₂ BrN ₃ S = 632.57) Sub 2-31 m / z = 720.09 (C ₄₅ H ₂₅ BrN ₂ OS = 721.66) Sub 2-32 m / z = 593.08 (C ₃₇ H ₂₄ BrNS = 594.56) Sub 2-33 m / z = 471.99 (C ₂₄ H ₁₃ BrN ₂ O ₂ S = 473.34) Sub 2-34 m / z = 503.03 (C ₃₀ H ₁₈ BrNS = 504.44) Sub 2-35 m / z = 477.02 (C ₂₈ H ₁₆ BrNS = 478.40) Sub 2-36 m / z = 508.07 (C ₃₀ H ₁₃ D ₅ BrNS = 509.47) Sub 2-37 m / z = 411.03 (C ₂₄ H ₁₄ BrNO = 412.28) Sub 2-38 m / z = 655.09 (C ₄₀ H ₂₂ BrN ₃ O ₂ = 656.53) Sub 2-39 m / z = 539.06 (C ₃₂ H ₁₈ BrN ₃ O = 540.41) Sub 2-40 m / z = 645.05 (C ₃₈ H ₂₀ BrN ₃ OS = 646.55) Sub 2-41 m / z = 461.04 (C ₂₈ H ₁₆ BrNO = 462.34) Sub 2-42 m / z = 487.06 (C ₃₀ H ₁₈ BrNO = 488.37) Sub 2-43 m / z = 537.07 (C ₃₄ H ₂₀ BrNO = 538.43) Sub 2-44 m / z = 437.08 (C ₂₇ H ₂₀ BrN = 438.36) Sub 2-45 m / z = 453.05 (C ₂₀ H ₂₀ BrNSi = 453.43) Sub 2-46 m / z = 474.95 (C ₂₄ H ₁₄ BrNSi = 478.24)

Sub 3 example

Meanwhile, the compound belonging to Sub 3 may be the following compound, but is not limited thereto, and Table 3 shows the FD-MS value of the compound belonging to Sub 3.

compound FD-MS compound FD-MS Sub 3-1 m / z = 287.11 (C ₁₈ H ₁₄ BNO ₂ = 287.12) Sub 3-2 m / z = 287.11 (C ₁₈ H ₁₄ BNO ₂ = 287.12) Sub 3-3 m / z = 287.11 (C ₁₈ H ₁₄ BNO ₂ = 287.12) Sub 3-4 m / z = 287.11 (C ₁₈ H ₁₄ BNO ₂ = 287.12) Sub 3-5 m / z = 337.13 (C ₂₂ H ₁₆ BNO ₂ = 337.18) Sub 3-6 m / z = 337.13 (C ₂₂ H ₁₆ BNO ₂ = 337.18) Sub 3-7 m / z = 337.13 (C ₂₂ H ₁₆ BNO ₂ = 337.18) Sub 3-8 m / z = 337.13 (C ₂₂ H ₁₆ BNO ₂ = 337.18) Sub 3-9 m / z = 337.13 (C ₂₂ H ₁₆ BNO ₂ = 337.18) Sub 3-10 m / z = 363.14 (C ₂₄ H ₁₈ BNO ₂ = 363.22) Sub 3-11 m / z = 363.14 (C ₂₄ H ₁₈ BNO ₂ = 363.22) Sub 3-12 m / z = 368.17 (C ₂₄ H ₁₃ D ₅ BNO ₂ = 368.25) Sub 3-13 m / z = 387.14 (C ₂₆ H ₁₈ BNO ₂ = 387.24) Sub 3-14 m / z = 437.16 (C ₃₀ H ₂₀ BNO ₂ = 437.30) Sub 3-15 m / z = 413.16 (C ₂₈ H ₂₀ BNO ₂ = 413.27) Sub 3-16 m / z = 429.13 (C ₂₈ H ₁₇ BFNO ₂ = 429.25) Sub 3-17 m / z = 368.17 (C ₂₄ H ₁₃ D ₅ BNO ₂ = 368.25) Sub 3-18 m / z = 482.18 (C ₃₁ H ₂₃ BNO ₃ = 482.34) Sub 3-19 m / z = 452.17 (C ₃₀ H ₂₁ BN ₂ O ₂ = 452.31) Sub 3-20 m / z = 364.14 (C ₂₃ H ₁₇ BN ₂ O ₂ = 364.20) Sub 3-21 m / z = 442.16 (C ₂₇ H ₁₉ BN ₄ O ₂ = 442.28) Sub 3-22 m / z = 441.16 (C ₂₈ H ₂₀ BN ₃ O ₂ = 441.29) Sub 3-23 m / z = 441.26 (C ₂₈ H ₂₀ BN ₃ O ₂ = 441.29) Sub 3-24 m / z = 442.16 (C ₂₇ H ₁₉ BN ₄ O ₂ = 442.28) Sub 3-25 m / z = 441.16 (C ₂₈ H ₂₀ BN ₃ O ₂ = 441.29) Sub 3-26 m / z = 517.20 (C ₃₄ H ₂₄ BN ₃ O ₂ = 517.38) Sub 3-27 m / z = 528.25 (C ₃₃ H ₁₃ D ₁₀ BN ₄ O ₂ = 528.43) Sub 3-28 m / z = 455.14 (C ₂₈ H ₁₈ BN ₃ O ₃ = 455.27) Sub 3-29 m / z = 505.16 (C ₃₂ H ₂₀ BN ₃ O ₃ = 505.33) Sub 3-30 m / z = 444.11 (C ₂₇ H ₁₇ BN ₂ O ₂ S = 444.31) Sub 3-31 m / z = 547.15 (C ₃₄ H ₂₂ BN ₃ O ₂ S = 547.43) Sub 3-32 m / z = 415.15 (C ₂₆ H ₁₈ BN ₃ O ₂ = 415.25) Sub 3-33 m / z = 465.16 (C ₃₀ H ₂₀ BN ₃ O ₂ = 465.31) Sub 3-34 m / z = 565.20 (C ₃₈ H ₂₄ BN ₃ O ₂ = 565.43) Sub 3-35 m / z = 465.16 (C ₃₀ H ₂₀ BN ₃ O ₂ = 465.31) Sub 3-36 m / z = 228.04 (C ₁₂ H ₉ BO ₂ S = 228.07) Sub 3-37 m / z = 228.04 (C ₁₂ H ₉ BO ₂ S = 228.07) Sub 3-38 m / z = 228.04 (C ₁₂ H ₉ BO ₂ S = 228.07) Sub 3-39 m / z = 278.06 (C ₁₆ H ₁₁ BN ₂ S = 278.13) Sub 3-40 m / z = 278.06 (C ₁₆ H ₁₁ BO ₂ S = 278.13) Sub 3-41 m / z = 278.06 (C ₁₆ H ₁₁ BO ₂ S = 278.13) Sub 3-42 m / z = 305.07 (C ₁₇ H ₁₂ BNO ₂ S = 305.16) Sub 3-43 m / z = 212.06 (C ₁₂ H ₉ BO ₃ = 212.01) Sub 3-44 m / z = 212.06 (C ₁₂ H ₉ BO ₃ = 212.01) Sub 3-45 m / z = 212.06 (C ₁₂ H ₉ BO ₃ = 212.01) Sub 3-46 m / z = 262.08 (C ₁₆ H ₁₁ BO ₃ = 262.07) Sub 3-47 m / z = 312.10 (C ₂₀ H ₁₃ BO ₃ = 312.13) Sub 3-48 m / z = 289.09 (C ₁₇ H ₁₂ BNO ₃ = 289.09) Sub 3-49 m / z = 238.12 (C ₁₅ H ₁₅ BO ₂ = 238.09) Sub 3-50 m / z = 238.12 (C ₁₅ H ₁₅ BO ₂ = 238.09) Sub 3-51 m / z = 266.15 (C ₁₇ H ₁₉ BO ₂ = 266.14) Sub 3-52 m / z = 362.15 (C ₂₅ H ₁₉ BO ₂ = 362.23) Sub 3-53 m / z = 438.18 (C ₃₁ H ₂₃ BO ₂ = 438.32) Sub 3-54 m / z = 360.13 (C ₂₄ H ₁₇ BO ₂ = 360.21) Sub 3-55 m / z = 410.15 (C ₂₉ H ₁₉ BO ₂ = 410.27) Sub 3-56 m / z = 254.09 (C ₁₄ H ₁₅ BO ₂ Si = 254.16) Sub 3-57 m / z = 254.09 (C ₁₄ H ₁₅ BO ₂ Si = 254.16) Sub 3-58 m / z = 282.12 (C ₁₆ H ₁₉ BO ₂ Si = 282.22) Sub 3-59 m / z = 378.12 (C ₂₄ H ₁₉ BO ₂ Si = 387.30) Sub 3-60 m / z = 378.12 (C ₂₄ H ₁₉ BO ₂ Si = 378.30) Sub 3-61 m / z = 376.11 (C ₂₄ H ₁₇ BO ₂ Si = 376.29) Sub 3-62 m / z = 275.99 (C ₁₂ H ₉ BO ₂ Se = 274.97) Sub 3-63 m / z = 275.99 (C ₁₂ H ₉ BO ₂ Se = 274.97) Sub 3-64 m / z = 326.00 (C ₁₆ H ₁₁ BO ₂ Se = 325.03)

Synthesis of Product of Formula 1

Put the Sub 1 or Sub 2 compound (1 eq) into the round bottom flask, and add the Sub 3 compound (1 eq), Pd (PPh ₃ ) ₄ (0.03 to 0.05 eq), NaOH (3 eq), THF (3 mL / 1 mmol) and water (1.5 mL / 1 mmol). Then, it was heated to reflux at 80 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Toluene and Acetone to obtain a product.

Synthesis of Compound 1-2

Round bottom flask Sub 1-2 (5g, 11.5mmol), Sub 3-3 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF Add (30 mL) / H ₂ O (15 mL). Then, the mixture was heated to reflux for 8 hours at 80 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from Toluene and Acetone to obtain product 1-2 (5.4 g, 80%).

Synthesis of Compound 1-7

Sub 1-3 (10g, 20mmol), Sub 3-3 (5.7g, 20mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (2.4g, 59mmol), THF (40mL) / H ₂ O (20mL) was obtained by using the above 1-2 synthesis method, product 1-7 (11.3g, 85%).

Synthesis of Compound 1-14

Sub 1-5 (10g, 21mmol), Sub 3-10 (7.6g, 21mmol), Pd (PPh ₃ ) ₄ (1g, 0.8mmol), NaOH (2.5g, 63mmol), THF (40mL) / H ₂ O (20mL) was obtained product 1-14 (12.3g, 82%) using the above 1-2 synthesis method.

Synthesis of Compound 1-20

Sub 1-1 (10g, 21mmol), Sub 3-11 (7.6g, 21mmol), Pd (PPh ₃ ) ₄ (1g, 0.8mmol), NaOH (2.5g, 63mmol), THF (40mL) / H ₂ O (20mL) was obtained product 1-20 (12.5g, 83%) using the above 1-2 synthesis method.

Synthesis of Compound 1-26

Sub 1-6 (5g, 11.5mmol), Sub 3-3 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30mL) / H ₂ O (15 mL) was obtained product 1-26 (4.9 g, 72%) using the above 1-2 synthesis method.

Synthesis of Compound 1-27

Sub 1-6 (5g, 11.5mmol), Sub 3-10 (4.2g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30mL) / H ₂ O (15 mL) was obtained using the above 1-2 synthesis method to obtain product 1-27 (6.5 g, 85%).

Synthesis of Compound 1-33

Sub 1-7 (10g, 20mmol), Sub 3-11 (7.3g, 20mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (2.4g, 59mmol), THF (40mL) / H ₂ O (20mL) was obtained by using the above 1-2 synthesis method, product 1-33 (13.5g, 91%).

Synthesis of Compound 1-51

Sub 1-6 (5g, 11.5mmol), Sub 3-1 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30mL) / H ₂ O (15 mL) was obtained product 1-51 (3.5 g, 51%) using the above 1-2 synthesis method.

Synthesis of Compound 1-52

Sub 1-6 (5g, 11.5mmol), Sub 3-2 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30mL) / H ₂ O (15 mL) was obtained using the 1-2 synthesis method above, and product 1-52 (3.8 g, 56%) was obtained.

Synthesis of Compound 1-53

Sub 1-6 (5g, 11.5mmol), Sub 3-4 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30mL) / H ₂ O (15 mL) was obtained product 1-53 (4.2 g, 62%) using the above 1-2 synthesis method.

Synthesis of Compound 1-66

Sub 1-14 (10g, 21mmol), Sub 3-3 (7.6g, 21mmol), Pd (PPh ₃ ) ₄ (1g, 0.8mmol), NaOH (2.5g, 63mmol), THF (40mL) / H ₂ O (20 mL) was obtained product 1-66 (8.5 g, 63%) using the above 1-2 synthesis method.

Synthesis of Compound 1-71

Round bottom flask Sub 1-1 (5g, 11.5mmol), Sub 3-46 (3.0g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained product 1-71 (4.7 g, 73%) using the above 1-2 synthesis method.

Synthesis of Compound 1-78

Round bottom flask Sub 1-4 (5g, 9.9mmol), Sub 3-53 (4.3g, 9.9mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.4mmol), NaOH (1.2g, 29.7mmol), THF (40 mL) / H ₂ O (20 mL) was obtained using the 1-2 synthesis method above to obtain product 1-78 (5.3 g, 65%).

Synthesis of Compound 1-90

Round bottom flask Sub 1-39 (10g, 20.5mmol), Sub 3-38 (5.9g, 20.5mmol), Pd (PPh ₃ ) ₄ (1g, 0.8mmol), NaOH (2.5g, 61mmol), THF ( 40 mL) / H ₂ O (20 mL) was obtained using the above 1-2 synthesis method to obtain product 1-90 (5.8 g, 48%).

Synthesis of Compound 2-1

Round bottom flask Sub 2-1 (5g, 11.5mmol), Sub 3-3 (3.9g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained using the above 1-2 synthesis method to obtain product 2-1 (5.5 g, 81%).

Synthesis of Compound 2-2

Round bottom flask Sub 2-1 (5g, 11.5mmol), Sub 3-10 (4.2g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained using the above 1-2 synthesis method to obtain product 2-2 (6.1 g, 80%).

Synthesis of Compound 2-3

Round bottom flask Sub 2-1 (5g, 11.5mmol), Sub 3-11 (4.2g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained product 2-3 (5.8 g, 76%) using the above 1-2 synthesis method.

Synthesis of Compound 2-6

Round bottom flask Sub 2-2 (10g, 20mmol), Sub 3-3 (5.7g, 20mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (2.4g, 59mmol), THF (40mL) ) / H ₂ O (20 mL) was obtained product 2-6 (10.3 g, 81%) using the above 1-2 synthesis method.

Synthesis of Compound 2-7

Round bottom flask Sub 2-2 (10g, 20mmol), Sub 3-10 (7.3g, 20mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (2.4g, 59mmol), THF (40mL) ) / H ₂ O (20 mL) was obtained product 2-7 (11 g, 74%) using the above 1-2 synthesis method.

Synthesis of Compound 2-8

Round bottom flask Sub 2-2 (10g, 20mmol), Sub 3-11 (7.3g, 20mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (2.4g, 59mmol), THF (40mL) ) / H ₂ O (20 mL) was obtained product 2-8 (12 g, 81%) using the above 1-2 synthesis method.

Synthesis of Compound 2-33

Round bottom flask Sub 2-1 (5g, 11.5mmol), Sub 3-38 (2.6g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained using the above 1-2 synthesis method to obtain product 2-1 (5.0 g, 82%).

Synthesis of Compound 2-38

Round bottom flask Sub 2-1 (5g, 11.5mmol), Sub 3-45 (2.4g, 11.5mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.5mmol), NaOH (1.4g, 35mmol), THF (30 mL) / H ₂ O (15 mL) was obtained using the above 1-2 synthesis method to obtain product 2-1 (4.4 g, 74%).

Synthesis of Compound 2-133

Round bottom flask Sub 2-37 (5g, 12mmol), Sub 3-10 (4.4g, 12mmol), Pd (PPh ₃ ) ₄ (0.6g, 0.5mmol), NaOH (1.5g, 36mmol), THF (30mL ) / H ₂ O (15 mL) was obtained product 2-133 (5.6 g, 72%) using the above 1-2 synthesis method.

compound FD-MS compound FD-MS 1-1 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-2 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-3 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-4 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-5 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-6 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-7 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-8 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-9 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-10 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-11 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-12 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-13 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-14 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-15 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-16 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-17 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-18 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-19 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-20 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-21 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-22 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-23 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-24 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-25 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-26 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-27 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-28 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-29 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-30 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-31 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-32 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-33 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-34 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-35 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-36 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 1-37 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-38 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-39 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-40 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-41 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-42 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-43 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-44 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-45 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-46 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-47 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-48 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 1-49 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-50 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 1-51 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-52 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-53 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 1-54 m / z = 531.11 (C ₃₆ H ₂₁ NS ₂ = 531.69) 1-55 m / z = 531.11 (C ₃₆ H ₂₁ NS ₂ = 531.69) 1-56 m / z = 515.13 (C ₃₆ H ₂₁ NOS = 515.62) 1-57 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 743.90) 1-58 m / z = 870.28 (C ₆₂ H ₃₈ N ₄ S = 871.06) 1-59 m / z = 768.23 (C ₅₄ H ₃₂ N ₄ S = 768.92) 1-60 m / z = 718.22 (C ₅₀ H ₃₀ N ₄ S = 718.87) 1-61 m / z = 931.30 (C ₆₈ H ₄₁ N ₃ S = 932.14) 1-62 m / z = 808.23 (C ₅₆ H ₃₂ N ₄ OS = 808.94) 1-63 m / z = 850.22 (C ₅₈ H ₃₄ N ₄ S ₂ = 851.05) 1-64 m / z = 831.32 (C ₅₇ H ₂₅ D ₁₀ N ₅ S = 832.05) 1-65 m / z = 768.23 (C ₅₄ H ₃₂ N ₄ S = 768.92) 1-66 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 1-67 m / z = 531.11 (C ₃₆ H ₂₁ NS ₂ = 531.69) 1-68 m / z = 708.17 (C ₄₉ H ₂₈ N ₂ S ₂ = 708.89) 1-69 m / z = 733.19 (C ₅₂ H ₃₁ NS ₂ = 733.94) 1-70 m / z = 708.17 (C ₄₉ H ₂₈ N ₂ S ₂ = 708.89) 1-71 m / z = 565.15 (C ₄₀ H ₂₃ NOS = 565.68) 1-72 m / z = 822.25 (C ₅₇ H ₃₄ N ₄ OS = 822.97) 1-73 m / z = 809.21 (C ₅₆ H ₃₁ N ₃ O ₂ S = 809.93) 1-74 m / z = 781.13 (C ₅₂ H ₃₁ NSSe = 780.83) 1-75 m / z = 681.08 (C4 ₂ H ₂₃ N ₃ SSe = 680.68) 1-76 m / z = 585.19 (C ₄₀ H ₃₁ NSSi = 585.83) 1-77 m / z = 809.23 (C ₅₆ H ₃₅ N ₃ SSi = 810.05) 1-78 m / z = 817.28 (C ₆₁ H ₃₉ NS = 818.03) 1-79 m / z = 817.26 (C ₅₉ H ₃₅ N ₃ S = 817.99) 1-80 m / z = 742.28 (C ₅₀ H ₃₀ N ₄ OS = 742.93) 1-81 m / z = 574.20 (C ₄₂ H ₂₆ N ₂ O = 574.67) 1-82 m / z = 624.22 (C ₄₆ H ₂₈ N ₂ O = 624.73) 1-83 m / z = 852.29 (C ₆₂ H ₃₆ N ₄ O = 852.98) 1-84 m / z = 834.25 (C ₅₈ H ₃₄ N ₄ OS = 834.98) 1-85 m / z = 649.24 (C ₄₉ H ₃₁ NO = 649.78) 1-86 m / z = 829.24 (C ₆₁ H ₃₅ NOS = 830.00) 1-87 m / z = 665.22 (C ₄₈ H ₃₁ NOSi = 665.85) 1-88 m / z = 563.08 (C ₃₆ H ₂₁ NOSe = 562.52) 1-89 m / z = 600.26 (C ₄₅ H ₃₂ N ₂ = 600.75) 1-90 m / z = 591.20 (C ₄₃ H ₂₉ NS = 591.76) 1-91 m / z = 525.21 (C ₃₉ H ₂₇ NO = 525.64) 1-92 m / z = 551.26 (C ₄₂ H ₃₃ N = 551.72) 1-93 m / z = 616.23 (C ₄₄ H ₃₂ N ₂ Si = 616.82) 1-94 m / z = 541.19 (C ₃₈ H ₂₇ NOSi = 541.71) 1-95 m / z = 557.16 (C ₃₈ H ₂₇ NSSi = 557.78) 1-96 m / z = 638.13 (C ₄₂ H ₂₆ N ₂ Se = 637.63) 1-97 m / z = 563.08 (C ₃₆ H ₂₁ NOSe = 562.52) 1-98 m / z = 589.13 (C ₃₉ H ₂₇ NSe = 588.60) 2-1 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-2 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-3 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-4 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-5 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-6 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-7 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-8 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-9 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-10 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-11 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-12 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-13 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-14 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-15 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-16 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-17 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-18 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-19 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-20 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-21 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-22 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-23 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-24 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-25 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-26 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-27 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-28 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-29 m / z = 746.28 (C ₅₄ H ₃₈ N ₂ S = 746.96) 2-30 m / z = 796.25 (C ₅₇ H ₃₆ N ₂ OS = 796.97) 2-31 m / z = 780.26 (C ₅₇ H ₃₆ N ₂ S = 780.97) 2-32 m / z = 743.24 (C ₅₃ H ₃₃ N ₃ S = 743.91) 2-33 m / z = 531.11 (C ₃₆ H ₂₁ NS ₂ = 531.69) 2-34 m / z = 607.14 (C ₄₂ H ₂₅ NS ₂ = 607.78) 2-35 m / z = 607.14 (C ₄₂ H ₂₅ NS ₂ = 607.78) 2-36 m / z = 581.13 (C ₄₀ H ₂₃ NS ₂ = 581.75) 2-37 m / z = 581.13 (C ₄₀ H ₂₃ NS ₂ = 581.75) 2-38 m / z = 515.13 (C ₃₆ H ₂₁ NOS = 515.62) 2-39 m / z = 591.17 (C ₄₂ H ₂₅ NOS = 591.72) 2-40 m / z = 591.17 (C ₄₂ H ₂₅ NOS = 591.72) 2-41 m / z = 565.15 (C ₄₀ H ₂₃ NOS = 565.68) 2-42 m / z = 565.15 (C ₄₀ H ₂₃ NOS = 565.68) 2-43 m / z = 541.19 (C ₃₉ H ₂₇ NS = 541.70) 2-44 m / z = 617.21 (C ₄₅ H ₃₁ NS = 617.80) 2-45 m / z = 617.21 (C ₄₅ H ₃₁ NS = 617.80) 2-46 m / z = 591.20 (C ₄₃ H ₂₉ NS = 591.76) 2-47 m / z = 591.20 (C ₄₃ H ₂₉ NS = 591.76) 2-48 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-49 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-50 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-51 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-52 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-53 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-54 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-55 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-56 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-57 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-58 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-59 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-60 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-61 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-62 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-63 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 2-64 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-65 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-66 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-67 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-68 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-69 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-70 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-71 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-72 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-73 m / z = 716.23 (C ₅₂ H ₃₂ N ₂ S = 716.89) 2-74 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-75 m / z = 690.21 (C ₅₀ H ₃₀ N ₂ S = 690.85) 2-76 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-77 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-78 m / z = 590.18 (C ₄₂ H ₂₆ N ₂ S = 590.73) 2-79 m / z = 581.13 (C ₄₀ H ₂₃ NS ₂ = 581.75) 2-80 m / z = 581.13 (C ₄₀ H ₂₃ NS ₂ = 581.75) 2-81 m / z = 515.13 (C ₃₆ H ₂₁ NOS = 515.62) 2-82 m / z = 591.17 (C ₄₂ H ₂₅ NOS = 591.72) 2-83 m / z = 591.17 (C ₄₂ H ₂₅ NOS = 591.72) 2-84 m / z = 565.15 (C ₄₀ H ₂₃ NOS = 565.68) 2-85 m / z = 565.15 (C ₄₀ H ₂₃ NOS = 565.68) 2-86 m / z = 541.19 (C ₃₉ H ₂₇ NS = 541.70) 2-87 m / z = 617.21 (C ₄₅ H ₃₁ NS = 617.80) 2-88 m / z = 617.21 (C ₄₅ H ₃₁ NS = 617.80) 2-89 m / z = 531.11 (C ₃₆ H ₂₁ NS ₂ = 531.69) 2-90 m / z = 607.14 (C ₄₂ H ₂₅ NS ₂ = 607.78) 2-91 m / z = 607.14 (C ₄₂ H ₂₅ NS ₂ = 607.78) 2-92 m / z = 591.20 (C ₄₃ H ₂₉ NS = 591.76) 2-93 m / z = 591.20 (C ₄₃ H ₂₉ NS = 591.76) 2-94 m / z = 745.23 (C ₅₁ H ₃₁ N ₅ S = 745.89) 2-95 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-96 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-97 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-98 m / z = 718.22 (C ₅₀ H ₃₀ N ₄ S = 718.87) 2-99 m / z = 745.23 (C ₅₁ H ₃₁ N ₅ S = 745.89) 2-100 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-101 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-102 m / z = 744.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 2-103 m / z = 718.22 (C ₅₀ H ₃₀ N ₄ S = 718.87) 2-104 m / z = 768.24 (C ₅₄ H ₃₂ N ₄ S = 768.92) 2-105 m / z = 834.25 (C ₅₈ H ₃₄ N ₄ OS = 834.98) 2-106 m / z = 900.24 (C ₆₂ H ₃₆ N ₄ S ₂ = 901.11) 2-107 m / z = 844.27 (C ₆₀ H ₃₆ N ₄ S = 845.02) 2-108 m / z = 847.25 (C ₆₀ H ₃ FN ₃ S = 848.00) 2-109 m / z = 745.23 (C ₅₁ H ₃₁ N ₅ S = 745.89) 2-110 m / z = 909.32 (C ₆₇ H ₃₅ D ₅ N ₂ S = 910.14) 2-111 m / z = 747.18 (C ₅₁ H ₂₉ N ₃ S ₂ = 747.93) 2-112 m / z = 762.29 (C ₅₄ H ₃₀ D ₅ N ₃ S = 762.97) 2-113 m / z = 789.25 (C ₅₉ H ₃₅ NS = 789.98) 2-114 m / z = 860.26 (C ₆₀ H ₃₆ N ₄ OS = 861.02) 2-115 m / z = 515.13 (C ₃₆ H ₂₁ NOS = 515.62) 2-116 m / z = 717.21 (C ₅₂ H ₃₁ NOS = 717.87) 2-117 m / z = 770.21 (C ₅₃ H ₃₀ N ₄ S = 770.90) 2-118 m / z = 845.25 (C ₆₀ H ₃₅ N ₃ OS = 846.00) 2-119 m / z = 699.14 (C ₄₆ H ₂₅ N ₃ S ₂ = 699.84) 2-120 m / z = 581.13 (C ₄₀ H ₂₃ NS ₂ = 581.75) 2-121 m / z = 785.20 (C ₅₄ H ₃₁ N ₃ S ₂ = 785.97) 2-122 m / z = 824.20 (C ₅₇ H ₃₂ N ₂ OS ₂ = 825.01) 2-123 m / z = 697.19 (C ₄₉ H ₃₁ NS ₂ = 697.91) 2-124 m / z = 624.04 (C ₃₆ H ₂₀ N ₂ O ₂ SSe = 623.58) 2-125 m / z = 666.21 (C ₄₈ H ₃₀ N ₂ S = 666.83) 2-126 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-127 m / z = 640.20 (C ₄₆ H ₂₈ N ₂ S = 640.79) 2-128 m / z = 671.24 (C ₄₈ H ₂₅ D ₅ N ₂ S = 671.86) 2-129 m / z = 671.24 (C ₄₈ H ₂₅ D ₅ N ₂ S = 671.86) 2-130 m / z = 557.16 (C ₃₈ H ₂₇ NSSi = 557.78) 2-131 m / z = 579.06 (C ₃₆ H ₂₁ NSSe = 579.58) 2-132 m / z = 681.19 (C ₄₈ H ₃₁ NSSi = 681.92) 2-133 m / z = 574.20 (C ₄₂ H ₂₆ N ₂ O = 574.67) 2-134 m / z = 650.24 (C ₄₈ H ₃₀ N ₂ O = 650.76) 2-135 m / z = 664.22 (C ₄₈ H ₂₈ N ₂ O ₂ = 664.75) 2-136 m / z = 818.27 (C ₅₈ H ₃₄ N ₄ O ₂ = 818.92) 2-137 m / z = 758.21 (C ₅₂ H ₃₀ N ₄ OS = 758.89) 2-138 m / z = 702.24 (C ₅₀ H ₃₀ N ₄ O = 702.80) 2-139 m / z = 729.25 (C ₅₁ H ₃₁ N ₅ O = 729.82) 2-140 m / z = 759.23 (C ₅₃ H ₃₃ N ₃ OS = 759.91) 2-141 m / z = 697.24 (C ₅₃ H ₃₁ NO = 697.82) 2-142 m / z = 739.23 (C ₅₄ H ₃₃ NOSi = 739.93) 2-143 m / z = 739.14 (C ₅₀ H ₂₉ NOSe = 738.73) 2-144 m / z = 650.27 (C ₄₉ H ₃₄ N ₂ = 650.81) 2-145 m / z = 591.20 (C ₄₃ H ₂₉ NO = 591.76) 2-146 m / z = 525.21 (C ₃₉ H ₂₇ NO = 525.64) 2-147 m / z = 551.26 (C ₄₂ H ₃₃ = 551.72) 2-148 m / z = 616.23 (C ₄₄ H ₃₂ N ₂ Si = 616.82) 2-149 m / z = 557.16 (C ₃₈ H ₂₇ NSSi = 557.78) 2-150 m / z = 541.19 (C ₃₈ H ₂₇ NOSi = 541.71) 2-151 m / z = 583.22 (C ₄₀ H ₃₃ NSi ₂ = 583.87) 2-152 m / z = 638.13 (C ₄₂ H ₂₆ N ₂ Se = 637.63) 2-153 m / z = 579.06 (C ₃₆ H ₂₁ NSSe = 578.58) 2-154 m / z = 589.13 (C ₃₉ H ₂₇ NSe = 588.60)

[Synthesis Example 2]

The compound represented by Chemical Formula (2) according to the present invention (final product 2) is prepared by reacting Sub 4 and Sub 5 as shown in Reaction Scheme 4 below.

<Reaction Scheme 4>

Sub 4 synthesis example

Sub 4 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto. (A and B are as defined in the above formula 2)

<Scheme 5>

1. Sub 4-1 Synthesis Example

(1) Sub 4-a-1 synthesis

1-bromonaphthalene (50.0 g, 241 mmol), bis (pinacolato) diboron (67.4 g, 266 mmol), KOAc (71 g, 724 mmol), PdCl ₂ (dppf) (5.30 g, 7.24 mmol) with DMF (1 L ) After being dissolved in a solvent, reflux was performed at 120 ° C for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After drying and concentrating the organic layer with MgSO ₄ , the resulting organic material was recrystallized using CH ₂ Cl ₂ and methanol solvent to obtain 45.4 g (yield: 74%) of the desired product.

(2) Sub 4-1b synthesis

Sub 4-a-1 (45.4 g, 179 mmol) obtained above, 1-bromo-2-nitrobenzene (36.1 g, 179 mmol), K ₂ CO ₃ (74.1 g, 536 mmol), Pd (PPh ₃ ) ₄ (12.4 g, 10.7 mmol) was added to a round bottom flask, THF (800 mL) and water (400 mL) were dissolved, and refluxed at 80 ° C. for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After drying and concentrating the organic layer with MgSO ₄ , the resulting organic material was separated using a silicagel column to obtain the desired product 37.0 g (yield: 83%).

(3) Sub 4-1 synthesis

Sub 4-b-1 (37.0 g, 148 mmol) and triphenylphosphine (97.3 g, 37.1 mmol) obtained above were dissolved in o- dichlorobenzene (800 mL) and refluxed at 200 ^o C for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was silicagel column and recrystallized to obtain 26.1 g (yield: 81%) of the desired product.

2. Sub 4-10 Synthesis Example

(1) Sub 4-a-10 synthesis

3-bromo-1,1'-biphenyl (50.0 g, 214 mmol), bis (pinacolato) diboron (59.9 g, 236 mmol), KOAc (63.2 g, 643 mmol), PdCl ₂ (dppf) (4.71 g, 6.43 mmol) was carried out in the same manner as the experimental method of Sub 4-a-1 to obtain 45.1 g (yield: 75%) of the product.

(2) Sub 4-b-10 synthesis

Sub 4-a-10 (45.1 g, 161 mmol) obtained above, 2-bromo-3-nitronaphthalene (40.6 g, 161 mmol), K ₂ CO ₃ (66.7 g, 483 mmol), Pd (PPh ₃ ) ₄ (11.2 g, 9.65 mmol) was carried out in the same manner as the experiment method for Sub 4-b-1 to obtain 44.0 g of product (yield: 84%).

(3) Sub 4-10 synthesis

Sub 4-b-10 (44.0 g, 135 mmol) and triphenylphosphine (88.6 g, 338 mmol) obtained above were carried out in the same manner as the experiment method for Sub 4-1 to obtain 34.5 g of product (yield: 87%). .

3. Sub 4-12 Synthesis Example

(1) Sub 4-c-12 synthesis

After dissolving 1-bromo-4-chlorobenzene (50.0 g, 261 mmol) in Toluene in a round bottom flask, 3-bromonaphthalen-2-amine (58.0 g, 261 mmol), Pd ₂ (dba) ₃ (7.17 g, 7.83 mmol), P ( t -Bu) ₃ (3.17 g, 15.7 mmol), NaO t -Bu (50.2 g, 522 mmol) was added and stirred at 100 ° C. When the reaction is completed, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 66.9 g (yield: 77%) of the product.

(2) Sub 4-d-12 synthesis

Sub 4-c-12 (66.9 g, 201 mmol) was added to DMA (400 mL) followed by Pd (OAc) ₂ (1.35 g, 6.03 mmol), K ₂ CO ₃ (83.4 g, 603 mmol), P ( t-Bu) ₃ H · BF ₄ (15.1 mL, 12.1 mmol) was added and stirred at 90 ° C. After the reaction is completed, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 43.0 g of product (yield: 85%).

(3) Sub 4-12 synthesis

Sub 4-d-12 (43.0 g, 171 mmol), 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole obtained above (63.1 g, 171 mmol), K ₂ CO ₃ (70.9 g, 513 mmol), Pd (PPh ₃ ) ₄ (11.9 g, 10.3 mmol) were carried out in the same manner as in Sub 4-b-1, and the product 68.2. g (yield: 87%).

4. Sub 4-18 Synthesis Example

(1) Sub 4-a-18 synthesis

1-bromonaphthalene (50.0 g, 241 mmol), bis (pinacolato) diboron (67.4 g, 266 mmol), KOAc (71.1 g, 724 mmol), PdCl ₂ (dppf) (5.30 g, 7.24 mmol) above Sub 4- The same procedure as in a-1 was used to obtain 44.2 g of product (yield: 72%).

(2) Sub 4-b-18 synthesis

Sub 4-a-18 (44.2 g, 174 mmol) obtained above, 1-bromo-2-nitronaphthalene (43.8 g, 174 mmol), K ₂ CO ₃ (72.1 g, 522 mmol), Pd (PPh ₃ ) ₄ (12.1 g, 10.4 mmol) was carried out in the same manner as the experiment method for Sub 4-b-1 to obtain 42.2 g of product (yield: 81%).

(3) Sub 4-18 synthesis

Sub 4-b-18 (42.2 g, 141 mmol) and triphenylphosphine (92.3 g, 352 mmol) obtained above were carried out in the same manner as the experimental method of Sub 4-1 to obtain 31.6 g of product (yield: 84%). .

5. Sub 4-35 Synthesis Example

(1) Sub 4-c-35 synthesis

1-bromonaphthalene (50.0 g, 241 mmol), 2-chloronaphthalen-1-amine (42.9 g, 241 mmol), Pd ₂ (dba) ₃ (6.63 g, 7.24 mmol), P ( t -Bu) ₃ (2.93 g , 14.5 mmol) and NaO t -Bu (46.4 g, 483 mmol) were performed in the same manner as in Sub 4-c-12, to obtain 52.1 g of product (yield: 71%).

(2) Sub 4-35 synthesis

Sub 4-c-35 (52.1 g, 171 mmol), Pd (OAc) ₂ (1.15 g, 5.14 mmol), K ₂ CO ₃ (71.1 g, 514 mmol), P (t-Bu) ₃ HBF ₄ (12.9 mL, 10.3 mmol) was carried out in the same manner as in Sub 4-d-12 to obtain 34.4 g of product (yield: 75%).

6. Sub 4-36 Synthesis Example

(1) Sub 4-a-36 synthesis

9-bromophenanthrene (50.0 g, 194 mmol), bis (pinacolato) diboron (54.3 g, 214 mmol), KOAc (57.3 g, 583 mmol), PdCl ₂ (dppf) (4.27 g, 5.83 mmol) above Sub 4- The same procedure as in a-1 was used to obtain 46.9 g of product (yield: 76%).

(2) Sub 4-b-36 synthesis

Sub 4-a-36 (46.9 g, 148 mmol) obtained above, 1-bromo-2-nitronaphthalene (37.3 g, 148 mmol), K ₂ CO ₃ (61.2 g, 443 mmol), Pd (PPh ₃ ) ₄ (10.3 g, 8.88 mmol) was carried out in the same manner as the experiment method of Sub 4-b-1 to obtain 41.9 g of product (yield: 81%).

(3) Sub 4-36 synthesis

Sub 4-b-36 (41.9 g, 120 mmol) and triphenylphosphine (78.6 g, 300 mmol) obtained above were carried out in the same manner as the experimental method for Sub 4-1 to obtain 28.2 g of product (yield: 74%). .

Examples of Sub 4 are as follows, but are not limited thereto, and Table 5 shows FD-MS (Field Desorption-Mass Spectrometry) values of compounds belonging to Sub 4.

compound FD-MS compound FD-MS Sub4-1 m / z = 217.09 (C ₁₆ H ₁₁ N = 217.27) Sub4-2 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-3 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-4 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-5 m / z = 369.15 (C ₂₈ H ₁₉ N = 369.47) Sub4-6 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-7 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-8 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-9 m / z = 217.09 (C ₁₆ H ₁₁ N = 217.27) Sub4-10 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-11 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-12 m / z = 458.18 (C ₃₄ H ₂₂ N ₂ = 458.56) Sub4-13 m / z = 217.09 (C ₁₆ H ₁₁ N = 217.27) Sub4-14 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-15 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-16 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-17 m / z = 293.12 (C ₂₂ H ₁₅ N = 293.37) Sub4-18 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-19 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-20 m / z = 419.17 (C ₃₂ H ₂₁ N = 419.53) Sub4-21 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-22 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-23 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-24 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-25 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-26 m / z = 419.17 (C ₃₂ H ₂₁ N = 419.53) Sub4-27 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-28 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-29 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-30 m / z = 419.17 (C ₃₂ H ₂₁ N = 419.53) Sub4-31 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-32 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-33 m / z = 343.14 (C ₂₆ H ₁₇ N = 343.43) Sub4-34 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) Sub4-35 m / z = 267.10 (C ₂₀ H ₁₃ N = 267.33) Sub4-36 m / z = 317.12 (C ₂₄ H ₁₅ N = 317.39) Sub4-37 m / z = 317.12 (C ₂₄ H ₁₅ N = 317.39) Sub4-38 m / z = 317.12 (C ₂₄ H ₁₅ N = 317.39) Sub4-39 m / z = 367.14 (C ₂₈ H ₁₇ N = 367.45)

Sub 5 example

Examples of Sub 5 of Scheme 4 are as follows and are not limited thereto.

compound FD-MS compound FD-MS Sub 5-1 m / z = 240.05 (C ₁₄ H ₉ ClN ₂ = 240.69) Sub 5-2 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-3 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-4 m / z = 316.08 (C ₂₀ H ₁₃ ClN ₂ = 316.79) Sub 5-5 m / z = 316.08 (C ₂₀ H ₁₃ ClN ₂ = 316.79) Sub 5-6 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-7 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-8 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-9 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-10 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-11 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-12 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-13 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-14 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-15 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-16 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-17 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-18 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-19 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-20 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-21 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-22 m / z = 480.14 (C ₃₃ H ₂₁ ClN ₂ = 481.00) Sub 5-23 m / z = 480.14 (C ₃₃ H ₂₁ ClN ₂ = 481.00) Sub 5-24 m / z = 480.14 (C ₃₃ H ₂₁ ClN ₂ = 481.00) Sub 5-25 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 5-26 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 5-27 m / z = 410.04 (C ₂₄ H ₁₅ BrN ₂ = 411.30) Sub 5-28 m / z = 410.04 (C ₂₄ H ₁₅ BrN ₂ = 411.30) Sub 5-29 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-30 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-31 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-32 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-33 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-34 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-35 m / z = 240.05 (C ₁₄ H ₉ ClN ₂ = 240.69) Sub 5-36 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-37 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-38 m / z = 316.08 (C ₂₀ H ₁₃ ClN ₂ = 316.79) Sub 5-39 m / z = 316.08 (C ₂₀ H ₁₃ ClN ₂ = 316.79) Sub 5-40 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-41 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-42 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-43 m / z = 346.03 (C ₂₀ H ₁₁ ClN ₂ S = 346.83) Sub 5-44 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-45 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-46 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-47 m / z = 330.06 (C ₂₀ H ₁₁ ClN ₂ O = 330.77) Sub 5-48 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-49 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-50 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-51 m / z = 405.10 (C ₂₆ H ₁₆ ClN ₃ = 405.89) Sub 5-52 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-53 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-54 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-55 m / z = 356.11 (C ₂₃ H ₁₇ ClN ₂ = 356.85) Sub 5-56 m / z = 480.14 (C ₃₃ H ₂₁ ClN ₂ = 481.00) Sub 5-57 m / z = 480.14 (C ₃₃ H ₂₁ ClN ₂ = 481.00) Sub 5-58 m / z = 478.12 (C ₃₃ H ₁₉ ClN ₂ = 478.98) Sub 5-59 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 5-60 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 5-61 m / z = 410.04 (C ₂₄ H ₁₅ BrN ₂ = 411.30) Sub 5-62 m / z = 410.04 (C ₂₄ H ₁₅ BrN ₂ = 411.30) Sub 5-63 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-64 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-65 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-66 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-67 m / z = 290.06 (C ₁₈ H ₁₁ ClN ₂ = 290.75) Sub 5-68 m / z = 366.09 (C ₂₄ H ₁₅ ClN ₂ = 366.85) Sub 5-69 m / z = 245.08 (C ₁₄ H ₄ D ₅ ClN ₂ = 245.72) Sub 5-70 m / z = 245.08 (C ₁₄ H ₄ D ₅ ClN ₂ = 245.72)

Synthesis example of Final products 2

After dissolving Sub 4 (1 eq) in a round bottom flask with Toluene, Sub 5 (1 eq), Pd ₂ (dba) ₃ (0.03 eq), P ( t -Bu) ₃ (0.06 eq), NaO t -Bu (2 eq.) Was added and stirred at 100 ° C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain Final product 2.

1. 3-1 Synthesis Example

Sub 4-1 (26.1 g, 120 mmol), Toluene (300 mL), Sub 5-1 (28.9 g, 120 mmol), Pd ₂ (dba) ₃ (3.30 g, 3.60 mmol), P ( t -Bu) ₃ (1.46 g, 7.21 mmol), NaO t -Bu (23.1 g, 240 mmol) was added and stirred at 100 ° C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 40.0 g of product (yield: 79%).

2. 3-18 Synthesis Example

Sub 4-10 (34.5 g, 118 mmol), Sub 5-35 (28.3 g, 118 mmol), Pd ₂ (dba) ₃ (3.23 g, 3.53 mmol), P ( t -Bu) ₃ (1.43 g, 7.06 mmol), NaO t -Bu (22.6 g, 235 mmol) was obtained 42.7 g (yield: 73%) of the final product using the synthesis method of 3-1.

3. 3-20 Synthesis Example

Sub 4-12 (68.2 g, 149 mmol), Sub 5-60 (53.7 g, 149 mmol), Pd ₂ (dba) ₃ (4.09 g, 4.46 mmol), P ( t -Bu) ₃ (1.81 g, 8.92 mmol), NaO t -Bu (28.6 g, 297 mmol) was obtained 83.5 g (yield: 76%) of the final product using the synthesis method of 3-1.

4. 3-31 Synthesis Example

Sub 4-18 (31.6 g, 118 mmol), Sub 5-7 (41.0 g, 118 mmol), Pd ₂ (dba) ₃ (3.25 g, 3.55 mmol), P ( t -Bu) ₃ (1.43 g, 7.09 mmol), NaO t -Bu (22.7 g, 236 mmol) was obtained 55.1 g (yield: 78%) of the final product using the synthesis method of 3-1.

5. 3-69 Synthesis Example

Sub 4-35 (34.4 g, 129 mmol), Sub 5-30 (47.2 g, 129 mmol), Pd ₂ (dba) ₃ (3.53 g, 3.86 mmol), P ( t -Bu) ₃ (1.56 g, 7.72 mmol), NaO t -Bu (24.7 g, 257 mmol) was obtained using the synthesis method of 3-1 above to obtain 53.1 g (yield: 69%) of the final product.

6. 3-73 Synthesis Example

Sub 4-36 (28.2 g, 88.8 mmol), Sub 5-69 (21.8 g, 88.8 mmol), Pd ₂ (dba) ₃ (2.44 g, 2.67 mmol), P ( t -Bu) ₃ (1.08 g, 5.33 mmol), NaO t -Bu (17.1 g, 178 mmol) was obtained 33.2 g (yield: 71%) of the final product using the synthesis method of 3-1.

compound FD-MS compound FD-MS 3-1 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-2 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-3 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-4 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-5 m / z = 573.22 (C ₄₂ H ₂₇ N ₃ = 573.70) 3-6 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-7 m / z = 573.22 (C ₄₂ H ₂₇ N ₃ = 573.70) 3-8 m / z = 573.22 (C ₄₂ H ₂₇ N ₃ = 573.70) 3-9 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-10 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-11 m / z = 573.22 (C ₄₂ H ₂₇ N ₃ = 573.70) 3-12 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-13 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-14 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-15 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-16 m / z = 603.18 (C ₄₂ H ₂₅ N ₃ S = 603.74) 3-17 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-18 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-19 m / z = 573.22 (C ₄₂ H ₂₇ N ₃ = 573.70) 3-20 m / z = 738.28 (C ₅₄ H ₃₄ N ₄ = 738.89) 3-21 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-22 m / z = 421.16 (C ₃₀ H ₁₉ N ₃ = 421.50) 3-23 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-24 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-25 m / z = 587.20 (C ₄₂ H ₂₅ N ₃ O = 587.68) 3-26 m / z = 497.19 (C ₃₆ H ₂₃ N ₃ = 497.60) 3-27 m / z = 587.20 (C ₄₂ H ₂₅ N ₃ O = 587.68) 3-28 m / z = 587.20 (C ₄₂ H ₂₅ N ₃ O = 587.68) 3-29 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-30 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-31 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-32 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-33 m / z = 673.25 (C ₅₀ H ₃₁ N ₃ = 673.82) 3-34 m / z = 653.19 (C ₄₆ H ₂₇ N ₃ S = 653.80) 3-35 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-36 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-37 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-38 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-39 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-40 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-41 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-42 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-43 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-44 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-45 m / z = 663.27 (C ₄₉ H ₃₃ N ₃ = 663.82) 3-46 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-47 m / z = 673.25 (C ₅₀ H ₃₁ N ₃ = 673.82) 3-48 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-49 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-50 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-51 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-52 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-53 m / z = 623.24 (C ₄₆ H ₂₉ N ₃ = 623.76) 3-54 m / z = 712.26 (C ₅₂ H ₃₂ N ₄ = 712.86) 3-55 m / z = 623.24 (C ₄₆ H ₂₉ N ₃ = 623.76) 3-56 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-57 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-58 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-59 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-60 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-61 m / z = 712.26 (C ₅₂ H ₃₂ N ₄ = 712.86) 3-62 m / z = 785.28 (C ₅₉ H ₃₅ N ₃ = 785.95) 3-63 m / z = 893.29 (C ₆₅ H ₃₉ N ₃ S = 894.11) 3-64 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-65 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-66 m / z = 471.17 (C ₃₄ H ₂₁ N ₃ = 471.56) 3-67 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-68 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-69 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-70 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-71 m / z = 547.20 (C ₄₀ H ₂₅ N ₃ = 547.66) 3-72 m / z = 597.22 (C ₄₄ H ₂₇ N ₃ = 597.72) 3-73 m / z = 526.22 (C ₃₈ H ₁₈ D ₅ N ₃ = 526.65) 3-74 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-75 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-76 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-77 m / z = 521.19 (C ₃₈ H ₂₃ N ₃ = 521.62) 3-78 m / z = 526.22 (C ₃₈ H ₁₈ D ₅ N ₃ = 526.65) 3-79 m / z = 571.20 (C ₄₂ H ₂₅ N ₃ = 571.68) 3-80 m / z = 571.20 (C ₄₂ H ₂₅ N ₃ = 571.68)

Manufacturing evaluation of organic electric devices

Example 1) Fabrication and test of red organic light emitting device

First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer first on the ITO layer (anode) formed on the glass substrate. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a thickness of 60 nm. Subsequently, N, N'-Bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as NPB) to a thickness of 60 nm. Vacuum-deposited to form a hole transport layer. As a host on the hole transport layer, a mixture of the above-described compounds represented by Chemical Formulas (1) and (2) in a ratio of 50:50 was used, and as a dopant, (piq) ₂ Ir (acac) [bis- (1- phenylisoquinolyl) iridium (Ⅲ) acetylacetonate] was deposited at a weight of 95: 5 to deposit a 30 nm thick light emitting layer on the hole transport layer. As the hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) is vacuum deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, an alkali metal halide as an electron injection layer, to a thickness of 0.2 nm, and then depositing Al to a thickness of 150 nm to use as a cathode.

[Comparative Examples 1 to 3]

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 1 was used alone as a host.

[Comparative Examples 4-7]

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 2 was used alone as a host.

[Comparative Example 8]

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 1 and Comparative Compound 1 were used as a mixture.

[Comparative Example 9, Comparative Example 10]

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 2 and Comparative Compound 2 or Comparative Compound 3 were used as a mixture.

The electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a direct bias DC voltage to the organic electroluminescent elements of the Examples and Comparative Examples prepared as described above, and the measurement result showed a luminance of 2500 cd / m2. T95 life was measured by a life measurement equipment manufactured by Max Science. The following table shows the results of device fabrication and evaluation.

Comparative Compound 1 Comparative Compound 2 Comparative Compound

Host 1 Host 2 Voltage Current Density Brightness
(cd / m2) Efficiency Lifetime
T (95) Comparative Example (1) Compound (1-56) - 5.1 19.5 2500 12.8 90.7 Comparative Example (2) Compound (2-43) - 5.2 22.1 2500 11.3 90.4 Comparative Example (3) Compound (2-133) - 5.0 18.5 2500 13.5 95.0 Comparative Example (4) Compound (3-6) - 4.6 13.0 2500 19.2 91.9 Comparative Example (5) Compound (3-10) - 4.3 13.3 2500 18.8 83.1 Comparative Example (6) Compound (3-25) - 4.3 14.5 2500 17.2 90.2 Comparative Example (7) Compound (3-26) - 4.1 14.9 2500 16.8 80.5 Comparative Example (8) Compound (2-133) Comparative Compound 1 4.5 12.1 2500 20.7 102.5 Comparative Example (9) Compound (3-25) Comparative Compound 2 4.3 9.1 2500 27.5 110.7 Comparative Example (10) Compound (3-25) Comparative Compound 3 4.1 9.8 2500 25.4 105.3 Example (1) Compound (1-56) Compound (3-6) 4.2 6.2 2500 40.2 128.0 Example (2) Compound (2-43) Compound (3-6) 4.1 6.0 2500 42.0 128.8 Example (3) Compound (2-133) Compound (3-6) 4.0 5.9 2500 42.3 132.2 Example (4) Compound (1-56) Compound (3-10) 4.0 6.3 2500 40.0 116.7 Example (5) Compound (2-43) Compound (3-10) 4.0 6.0 2500 41.8 116.9 Example (6) Compound (2-133) Compound (3-10) 3.8 5.9 2500 42.1 119.1 Example (7) Compound (1-56) Compound (3-13) 4.1 6.7 2500 37.5 129.6 Example (8) Compound (2-43) Compound (3-13) 4.1 6.5 2500 38.5 130.5 Example (9) Compound (2-133) Compound (3-13) 3.9 6.2 2500 40.1 131.4 Example (10) Compound (1-56) Compound (3-18) 3.9 6.9 2500 36.1 114.9 Example (11) Compound (2-43) Compound (3-18) 3.7 6.7 2500 37.3 116.2 Example (12) Compound (2-133) Compound (3-18) 3.7 6.3 2500 39.4 118.8 Example (13) Compound (1-56) Compound (3-25) 4.0 6.8 2500 36.8 129.1 Example (14) Compound (2-43) Compound (3-25) 3.9 6.6 2500 37.7 130.7 Example (15) Compound (2-133) Compound (3-25) 3.9 6.6 2500 37.9 131.0 Example (16) Compound (1-56) Compound (3-26) 3.8 7.1 2500 35.4 115.8 Example (17) Compound (2-43) Compound (3-26) 3.8 6.7 2500 37.1 116.2 Example (18) Compound (2-133) Compound (3-26) 3.6 6.7 2500 37.5 119.4

As can be seen from the results in Table 8, when the material for an organic electroluminescent device of the present invention represented by Formula 1 and Formula 2 is mixed and used as a phosphorescent host (Examples 1 to 18), a device using a single material (Comparative Example) It was confirmed that the driving voltage, efficiency and lifespan were significantly improved compared to the devices (Comparative Examples 8 to 10) used by mixing 1 to 7) and a comparative compound.

In other words, when the compound of the present invention represented by Chemical Formula 1 and Chemical Formula 2 is used alone as a phosphorescent host, Comparative Examples 8 to 10 used as a phosphorescent host by mixing Comparative Compound 1 or Comparative Compound 2 rather than (Comparative Examples 1 to 7) The results of the results were generally excellent in terms of efficiency and life, and rather, Examples 1 to 18 in which the compounds of the present invention represented by Formula 1 and Formula 2 were mixed show remarkably excellent effects in terms of driving voltage, efficiency and life. Able to know.

Based on the results of the experiment, the present inventors judged that, in the case of a substance in which the substance of Formula 1 and the substance of Formula 2 are mixed, they have novel characteristics other than the characteristics of each substance, and thus the substance of Formula 1 and the substance of Formula 2 , PL and PL lifetime were measured using the mixture of the present invention, respectively. As a result, when the compounds of the present invention, Formula 1 and Formula 2 were mixed, it was confirmed that a new PL wavelength was formed unlike that of a single compound, and the decrease and extinction time of the newly formed PL wavelength was determined for each of Formula 1 and Formula 2 materials. It was confirmed that it was increased than the reduction and extinction time. When the compound of the present invention is used in combination, not only electrons and holes are moved through the energy level of each substance, but also electrons, hole movement or energy due to exciplex of new regions having new energy levels formed due to mixing. It is judged that the efficiency and life of the furnace are increased. As a result, when using the mixture of the present invention, it can be said that the mixed thin film is an important example of exciplex energy transfer and luminescence processes.

In addition, the reason why the combination of the present invention is superior to Comparative Examples 8 to 10 used as a phosphorescent host mixed with a comparative compound is not only electron but also a polycyclic ring compound represented by Chemical Formula 2, which is characterized by high hole stability and high T1. When the compound represented by Chemical Formula 1 having strong hole characteristics is mixed, the electron blocking ability is improved due to the high T1 and high LUMO energy values, and more holes move quickly and easily in the light emitting layer. Accordingly, it is judged that the charge balance in the light emitting layer of holes and electrons is increased, so that light emission is performed well inside the light emitting layer rather than the hole transport layer interface, thereby reducing deterioration at the HTL interface, thereby maximizing the driving voltage, efficiency, and lifetime of the entire device. . That is, the combination of Chemical Formula 1 and Chemical Formula 2 is thought to improve the performance of the entire device by synergistically electrochemically.

Example 2) Fabrication and test of red organic light emitting device by mixing ratio

Host 1 Host 2` Mixing ratio Voltage Current Density Brightness Efficiency Lifetime (1st host: 2nd host) (cd / m2) T (95) Example (19) Compound (1-56) Compound (3-6) 2: 8 4.0 6.4 2500 38.9 115.1 Example (20) Compound (1-56) Compound (3-6) 3: 7 4.1 6.4 2500 39.1 121.2 Example (21) Compound (1-56) Compound (3-6) 4: 6 4.1 6.3 2500 39.4 126.1 Example (22) Compound (2-133) Compound (3-26) 2: 8 3.4 6.9 2500 36.1 112.3 Example (23) Compound (2-133) Compound (3-26) 3: 7 3.4 6.8 2500 36.5 117.7 Example (24) Compound (2-133) Compound (3-26) 4: 6 3.6 6.7 2500 37.1 118.3

As shown in Table 9, the mixture of the compounds of the present invention was measured by fabricating the device by ratio (2: 8, 3: 7, 4: 6).

When the results were described in detail, it was confirmed that as the second host ratio increased, the result of the driving voltage was further improved, but, on the contrary, it was confirmed that the opposite tendency was observed in efficiency and life. Therefore, in the case of a mixture, it is judged that it is a very important task to derive a mixing ratio in which the charge balance in the light emitting layer is maximized because the amount of the mixing ratio affects the characteristics.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: organic electrical element 110: substrate
120: first electrode (anode) 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)

Claims (17)

An organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer (1). An organic electric device comprising a first host compound represented by and a second host compound represented by the formula (2).
Formula (1) Formula (2)

{In the formulas (1) and (2) above,
1) X and Y are each independently O; S; CR'R ";SiR'R" or Se ;,
2) a and b are each independently 0 or 1, provided that a + b is 1 or more,
3) R 'and R "are each independently hydrogen; an alkyl group of C ₁ to C ₅₀ ; an aryl group of C ₆ to C ₆₀ ; and a heteroaryl group of C ₂ to C ₆₀ ; or R' And R "form a ring with each other to form a spiro ring,
4) L ¹ , L ² and L 'are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Or a C ₂ ~ C ₆₀ heteroarylene group; and
5) Ar ¹ and Ar ² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-NR'R ";
6) Z is NR ', O, S, CR'R ", SiR'R", or Se,
7) R ¹ to R ⁶ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
R _a and R _b are independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom; is selected from the group consisting of,
When l, m, n, o, p, and q are 2 or more, they are the same as or different from each other, and a plurality of R ¹ , a plurality of R ² , a plurality of R ³ , a plurality of R ⁴ , and a plurality of R ^{5 to} each other, a plurality of R ^{6 to} each other can be combined to form an aromatic and heteroaromatic ring,
8) The A and B rings are each independently an aryl group of C ₆ to C ₆₀ or a heteroaryl group of C ₂ to C ₆₀ , and one of A and B is an aryl group of C ₁₀ to C ₆₀ ,
9) n, l, p and q are any integers from 0 to 4, m is 0 or 1, o is any integer from 0 to 3,
10) One of X ¹ and X ² is N and the other is C-Ar ² ,
Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio; Alkoxyl group of C ₁ -C ₂₀ ; C ₁ -C ₂₀ alkyl group; Alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ Aryl group; A C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group and C ₈ -C ₂₀ arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, also, these substituents may combine with each other to form a ring, wherein ''Cycle' means a C ₃ -C ₆₀ aliphatic ring or a C ₆ -C ₆₀ aromatic ring or a C ₂ -C ₆₀ heterocycle or a combination thereof, and includes a saturated or unsaturated ring.}
The organic electric device according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (3) or (4).
Formula (3) Formula (4)

(In the formulas (3) and (4), X, Y, Z, Ar ¹ , L ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , l, m, n, o, and p are It is the same as defined in claim 1 above.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas (5) to (12).
Formula (5) Formula (6) Formula (7) Formula (8)

Formula (9) Formula (10) Formula (11) Formula (12)

(In the formulas (5) to (12), X, Y, Z, Ar ¹ , L ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , l, m, n, o, and p are It is the same as defined in claim 1 above.)
The method of claim 1, wherein the l, m, n, o and p are all 0 organic electric device characterized in that The method according to claim 1, wherein any one of the R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an organic electric device characterized in that a pair of neighboring one another combine to form a ring. According to claim 1, wherein the X or Y is an organic electric device, characterized in that S or O
The method of claim 1, wherein the formula (1) is an organic electric device, characterized in that any one of the following compounds

The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (2) is represented by the following formula (13) or (14).
Formula (13) Formula (14)

(In the formulas (13) and (14), A, B, L ² , Ar ² , R ⁶ and q are the same as defined in claim 1 above.)
The organic electroluminescent device according to claim 1, wherein the A and B rings of the compound represented by the formula (2) are any one of the following (A-1) to (A-9).
(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)

(A-8) (A-9)

(In the formulas (A-1) to (A-9), R ¹⁰ is the same as R ^{1 in} claim 1,
* Indicates the bonding position of the A and B rings.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (2) is represented by any one of the following formulas (15) to (28).
Formula (15) Formula (16) Formula (17)

Formula (18) Formula (19) Formula (20)

Formula (21) Formula (22) Formula (23)

Formula (24) Formula (25) Formula (26)

Formula (27) Formula (28)

(In the formulas (15) to (28),
L ² , X ¹ , X ² , R ⁶ and q are the same as defined in claim 1 above,
R ¹² and R ¹³ are the same as R ¹ , defined in claim 1 above,
s and u are each independently an integer from 0 to 6,
t is an integer from 0 to 4,
v and w are each independently an integer of 0 to 8.)
The organic electroluminescent device according to claim 1, wherein R ⁶ of the compound represented by the formula (2) is hydrogen.
The method of claim 1, wherein the formula (2) is an organic electric device, characterized in that one of the following compounds

The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a ratio of any one of 1: 9 to 9: 1 by weight.
The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a weight ratio of 1: 9 to 5: 5.
The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a weight ratio of 2: 8 to 3: 7.
An electronic device comprising: a display device comprising the organic electroluminescent device according to claim 1 and a control unit driving the display device.
17. The electronic device according to claim 16, wherein the organic electric element is at least one of an organic electroluminescent element, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting element.

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