KR102611419B1 - 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 that can improve the luminous efficiency, stability, and lifespan of the device, an organic electric device using the same, and an electronic device thereof.

Description

Compounds for organic electric devices, organic electric devices using the same, and their electronic devices {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to compounds for organic electric devices, organic electric devices using the same, and electronic devices thereof.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic electric devices that utilize the organic light emission phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic electric device, and may be composed 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 organic layers in organic electric devices can 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 their function.

In the case of non-type cyclic compounds containing heteroatoms, the difference in properties depending on the material structure is very large, so they are applied to various layers as materials for organic electric devices. In particular, it has different characteristics such as band gap (HOMO, LUMO), electrical properties, chemical properties, and physical properties depending on the number of rings, fused position, and type and arrangement of heteroatoms, so it is being developed for application to various layers of organic electric devices using this. This has been going on.

In phosphorescent organic electric devices using phosphorescent dopant materials, the LUMO and HOMO levels of the host material are factors that have a significant impact on the efficiency and lifespan of the organic electric devices and determine whether electron and hole injection in the light-emitting layer can be efficiently controlled. Accordingly, it is possible to control the charge balance within the light-emitting layer and prevent a decrease in efficiency and lifespan due to quenching of dopant and light emission at the hole transport layer interface.

In the case of host materials for fluorescence and phosphorescence, research has recently been conducted on increasing the efficiency and lifespan of organic electric devices using TADF (Thermal activatied delayed fluorescent) and Exciplex, and in particular, identifying energy transfer methods from host materials to dopant materials. A lot of research is underway.

There are several methods to identify energy transfer within the emitting layer for TADF (Thermal activated delayed fluorescent) and exciplex, but it can be easily confirmed using the PL lifetime (TRTP) measurement method.

TRTP (Time resolved transient PL) measurement method is a method of observing the decrease in spectrum over time (decay time) after irradiating a pulse light source to the host thin film. It can identify the energy transfer method through observation of energy transfer and emission delay time. It is a measurement method. The TRTP measurement is a measurement method that can distinguish between fluorescence and phosphorescence, energy transfer method within mixed host materials, exciplex energy transfer method, and TADF energy transfer method.

As such, there are various factors that affect efficiency and lifespan depending on the way energy is transferred from the host material to the dopant material, and the energy transfer method is different depending on the material, so the development of stable and efficient host materials for organic electric devices is still needed. This has not been achieved sufficiently. Therefore, the development of new materials continues to be required, and in particular, the development of host materials for the light-emitting layer is urgently needed.

KR 101170666 B1

The present invention was proposed to solve the problems of the phosphorescent host material as described above, and is designed to control the charge balance, efficiency, and lifespan in the light-emitting layer by adjusting the HOMO level of the host material of the phosphorescent organic electric device containing a phosphorescent dopant. The purpose is to provide organic electric devices and electronic devices using compounds that can be improved.

The present invention reduces the energy barrier between the light-emitting layer and the adjacent layer by containing a specific first host material in combination with a specific second host material as the main component to control efficient hole injection in the light-emitting layer of a phosphorescent organic electric device. This provides high efficiency and long lifespan of organic electric devices by maximizing the charge balance within the light emitting layer.

The present invention relates to 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 having the chemical formula Provided is an organic electric device comprising a first host compound represented by formula (1) and a second host compound represented by formula (2).

Additionally, the present invention provides an organic electric device and an electronic device using the compounds represented by the above formulas.

By using the mixture according to the present invention as a phosphorescent host material, high luminous efficiency and low driving voltage of organic electric devices can be achieved, and the lifespan of the device can be greatly improved.

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

Hereinafter, the present invention will be described in detail with reference to embodiments. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

Additionally, when describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish 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 or connected to that other component, but there is another component between each component. It will be understood that elements may be “connected,” “combined,” or “connected.”

As used in this specification and the appended claims, unless otherwise noted, the following terms have the following meanings:

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl), or iodine (I), unless otherwise specified.

As used in the present invention, the term "alkyl" or "alkyl group", unless otherwise specified, has a single bond of 1 to 60 carbon atoms, and includes straight chain alkyl group, branched chain alkyl group, cycloalkyl (cycloaliphatic) group, and alkyl-substituted cyclo. It refers to radicals of saturated aliphatic functional groups, including alkyl groups and cycloalkyl-substituted alkyl groups.

As used in the present invention, the term “haloalkyl group” or “halogenalkyl group” means an alkyl group substituted with halogen, unless otherwise specified.

The term “heteroalkyl group” used in the present invention means that one or more of the carbon atoms constituting the alkyl group are replaced with a heteroatom.

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

The term “cycloalkyl” used in the present invention refers to alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

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

As used in the present invention, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refers to an alkenyl group to which an oxygen radical is attached, and, unless otherwise specified, refers to an alkenyl group having an oxygen radical attached thereto. It has a carbon number of, and is not limited to this.

The term “aryloxyl group” or “aryloxy group” used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

The terms “aryl group” and “arylene group” used in the present invention each have 6 to 60 carbon atoms unless otherwise specified, and are not limited thereto. In the present invention, an aryl group or arylene group refers to an aromatic group of a single ring or multiple rings, and includes an aromatic ring formed by combining adjacent substituents or participating in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a dimethyl fluorene group, a diphenyl fluorene group, or a spirofluorene group.

The prefix “aryl” or “ar” refers to 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 the carbon number described in this specification.

Additionally, when prefixes are named consecutively, it means that the substituents are listed in the order they are listed first. For example, an arylalkoxy group refers to an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group refers to a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group refers to an alkenyl group substituted with an arylcarbonyl group. And here, 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 in the present invention, the term “heteroaryl group” or “heteroarylene group” refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing one or more heteroatoms, unless otherwise specified. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" used in the present invention, unless otherwise specified, contains one or more heteroatoms, has a carbon number of 2 to 60, includes at least one of a single ring and a multiple ring, and includes a heteroaliphatic ring and a heterocyclic group. Contains an aromatic ring. It may also be formed by combining neighboring functional groups.

As used herein, the term “heteroatom” refers to N, O, S, P or Si, unless otherwise specified.

Additionally, the “heterocyclic group” may also include a ring containing SO ₂ instead of carbon forming the ring. For example, “heterocyclic group” includes the following compounds:

Unless otherwise specified, the term "aliphatic" used in the present invention refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "aliphatic ring" refers to 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 heterocycle having 2 to 60 carbon atoms, or a fused ring consisting of a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-described heterocompounds include one or more heteroatoms, 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 with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and 3 to 30 carbon atoms. It is a cycloalkyl group, an alkenyl group with 2 to 20 carbon atoms, an alkynyl group with 2 to 20 carbon atoms, or a combination thereof.

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

Also, unless explicitly stated otherwise, in the term “substituted or unsubstituted” used in the present invention, “substituted” refers to deuterium, halogen, amino group, nitrile group, nitro group, C ₁ to C ₂₀ alkyl group, C ₁ to 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, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ to C ₂₀ heterocyclic group, but is not limited to these substituents.

Additionally, unless explicitly stated otherwise, the chemical formula used in the present invention is applied identically to the substituent definition by the index definition in the following chemical formula.

Here, when a is an integer of 0, it means that the substituent R ¹ is absent. That is, when a is 0, it means that hydrogen is bonded to all the carbons forming the benzene ring. In this case, the hydrogen bonded to the carbon is indicated as You can omit it and write the chemical formula or compound. When a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, each substituent R 1 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 is bonded to the carbon of the benzene ring in a similar manner, and the indication of the hydrogen bonded to the carbon forming the benzene ring is omitted.

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

The present invention relates to 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 having the chemical formula Provided is an organic electric device comprising a first host compound represented by formula (1) and a second host compound represented by formula (2).

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

1) W, 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 selected from the group consisting of hydrogen; C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; and C ₂ ~ C ₆₀ heteroaryl group; 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;

5) Ar ¹ and Ar ² are each independently hydrogen; heavy hydrogen; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxyl 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; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b );

R _a and R _b are each independently an aryl group of C ₆ to C ₆₀ ; fluorenyl group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

When l, m, n, o and ^p are 2 or more, each ^is a ^plurality and is the same or different from each other and is adjacent to ^each other. ⁵ groups and a plurality of R ⁶ groups can combine with each other to form aromatic and heteroaromatic rings,

8) R ¹² , R ¹³ and R ¹⁴ are each independently hydrogen; heavy hydrogen; halogen; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b );

When g, h and i are 2 or more, they are each plural, the same or different from each other, and a plurality of adjacent R ^12s , a plurality of R ^13s , and a plurality of R ^14s can combine with each other to form aromatic and heteroaromatic rings,

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

10) g and i are any integer from 0 to 4, h is any integer from 0 to 2,

11) Two adjacent * in the formula (2) combine with * in the formula (2-1) to form a ring,

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 contain deuterium; halogen; Silane group; siloxane group; boron group; Germanium group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₂₀ aryl group; 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, and these substituents may be combined with each other to form a ring, where ''Ring' refers to a fused ring consisting of a C ₃ -C ₆₀ aliphatic ring, a C ₆ -C ₆₀ aromatic ring, a C ₂ -C ₆₀ heterocycle, or a combination thereof, and includes saturated or unsaturated rings.}

In the present invention, the compound represented by the above formula (1) provides an organic electric device containing a compound represented by the following formula (3) or (4).

^{( In the} above formulas ( ³ ) ^{and ( 4} ), Same as defined above)

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

^{( In the} above formulas ( ⁵ ) ^{to ( 12} ), Same as defined above)

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

As another example, the present invention is an organic electric device comprising a compound in which any one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ in Formula (1) combines with each other to form a ring. provides.

In addition, the present invention provides an organic electric device including a compound in Formula (1), where X and Y are S or O.

As a specific example, in the present invention, Formula (1) includes the following compounds.

Meanwhile, the present invention provides an organic electric device in which the compound represented by the above formula (2) includes a compound represented by any one of the following formulas (13) to (17).

Formula (13) Formula (14) Formula (15) Formula (16) Formula (17)

(In the above formulas (13) to (17), Ar ² , L ² , R ⁶ , g, h, i, q, R' and R" are as defined above,

R ^12' , R ^13' and R ^14' are the same as the definitions of R ¹² , R ¹³ and R ¹⁴ above.)

As another example, the present invention includes the compound represented by the formula (2) above, and a compound represented by any one of the following formulas (18) to (63).

Formula (18) Formula (19) Formula (20) Formula (21)

Formula (22) Formula (23) Formula (24) Formula (25)

Formula (26) Formula (27) Formula (28) Formula (29)

Formula (30) Formula (31) Formula (32) Formula (33)

Formula (34) Formula (35) Formula (36) Formula (37)

Formula (38) Formula (39) Formula (40) Formula (41)

Formula (42) Formula (43) Formula (44) Formula (45)

Formula (46) Formula (47) Formula (48) Formula (49)

Formula (50) Formula (51) Formula (52) Formula (53)

Formula (54) Formula (55) Formula (56) Formula (57)

Formula (58) Formula (59) Formula (60) Formula (61)

Formula (62) Formula (63)

(In the above formulas (18) to (63), Ar ² , L ² , R ⁶ , R ^12' , R ^13' , R ^14' , g, h, i, q and W are as defined above,

t is any integer from 0 to 4, and s and u are each independently any integer from 0 to 6.)

The compound according to claim 1, wherein all R6 of the compound represented by formula (2) are hydrogen.

As a specific example, in the present invention, Formula (2) includes the following compounds.

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 a substrate 110. (180) An organic material layer containing compounds represented by Chemical Formulas 1 and 2 is provided therebetween. At this time, the first electrode 120 may be an anode and the second electrode 180 may be a cathode. In the case of the inverted type, the first electrode may be the cathode and the second electrode may be the anode.

The organic layer sequentially includes 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 be included. At this time, the remaining layers except for the light emitting layer 150 may not be formed. It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and an electron transport layer 160, etc. may 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 at least one side of the first electrode and the second electrode opposite to the organic layer. The compound containing Formula 1 of the present invention can be used as a material for a light efficiency improvement layer or a protective layer.

Meanwhile, even if it is the same core, the band gap, electrical properties, and interface properties may vary depending on which substituent is attached to which position, so the selection of the core and the combination of sub-substituents attached to it are very important. It is important, and in particular, when the energy level and T1 value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, long lifespan and high efficiency can be achieved at the same time.

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

Accordingly, the present invention provides an organic electric device in which the compounds represented by the formula (1) and the formula (2) are mixed in a ratio of 1:9 to 9:1 and included in the light-emitting layer, preferably is included in the light emitting layer by mixing in a ratio of 1:9 to 5:5, more preferably in a ratio of 2:8 to 3:7.

The present invention further includes a light efficiency improvement 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 in the organic electric device. Organic electric devices are provided.

In addition, in the present invention, the organic material layer is formed by any one of a spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, and 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 formation method.

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

WOLED (White Organic Light Emitting Device) has the advantage of being easy to achieve high resolution and having excellent fairness, while being manufactured using the color filter technology of existing LCDs. Various structures for white organic light emitting devices, mainly used as backlight devices, are being proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are arranged in parallel with each other in a plane, and a stacking method in which R, G, and B light emitting layers are stacked top and bottom. There is a color conversion material (CCM) method that uses electroluminescence by a blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom, and the present invention. can be applied to these WOLEDs as well.

In addition, the present invention provides a display device including the above-described organic electric device; and a control unit that drives the display device.

In another aspect, the present invention provides an electronic device wherein the organic electric 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 consoles, various TVs, and various computers.

Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (2) of the present invention and the manufacturing examples of the organic electric devices of the present invention will be described in detail through examples. It is not limited.

[Synthesis Example 1]

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

<Scheme 1>

1. Example of synthesis of Sub 1

Sub 1 of Scheme 1 can be synthesized through the reaction route of Scheme 2 below, but is not limited thereto.

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

Examples of synthesis 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

In a round bottom flask, 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) mmol), NaO(t-Bu) (126g, 1317mmol), and Toluene (1.5L). Then, it is heated and refluxed at 70°C for 4 hours. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain the product Sub 1-I-1 (135 g, 79%).

Synthesis of Sub 1-II-1

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

Synthesis of Sub 1-1

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) in a round bottom flask. , 8.7mmol), NaO(t-Bu) (25g, 261mmol), and Toluene (300mL) are added. Then, it is heated and refluxed at 110°C for 8 hours. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain 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

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) in a round bottom flask. ), NaO(t-Bu) (24.6g, 255mmol), and Toluene (240mL) were 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

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) in a round bottom flask. -Bu) ₃ (1.8g, 8.7mmol), NaO(t-Bu) (25g, 261mmol), and Toluene (300mL) were used to obtain the product Sub 1-3 (32g, 74%) using the synthesis method of Sub 1-1 above. ) was obtained.

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

Synthesis of Sub 1-5

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) in a round bottom flask. , 8.7mmol), NaO(t-Bu) (25g, 261mmol), and Toluene (300mL) were used to obtain the product Sub 1-5 (29.1g, 70%) using the synthesis method of Sub 1-1.

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

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

In a round bottom flask, 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) (42g, 439mmol), and Toluene (500mL) were used to obtain the product Sub 1-I-6 (46g, 90%) using the above Sub 1-I-1 synthesis method.

Synthesis of Sub 1-II-6

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

Synthesis of Sub 1-6

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) in a round bottom flask. ), NaO(t-Bu) (8.2g, 85mmol), and Toluene (80mL) were used to obtain the product Sub 1-6 (10g, 84%) using the synthesis method of Sub 1-1.

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

Synthesis of Sub 1-7

Sub 1-II-6 (10g, 28mmol), 4-Iodo-1,1'-biphenyl (9.5g, 34mmol), Pd ₂ (dba) ₃ (1g, 1.1mmol), P(t-) in a round bottom flask. Bu) ₃ (0.6g, 2.8mmol), NaO(t-Bu) (8.2g, 85mmol), and Toluene (80mL) were used to synthesize the product Sub 1-7 (10g, 71%) using the synthesis method of Sub 1-1. ) was obtained.

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

Synthesis of Sub 1-I-14

In a round bottom flask, 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), and Toluene (500mL) were used to obtain the product Sub 1-I-14 (48g, 75%) using the above synthesis method of Sub 1-I-1. got it

Synthesis of Sub 1-II-14

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

Synthesis of Sub 1-14

In a 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), and Toluene (300mL) are added. Then, heated and refluxed at 110°C for 8 hours. When the reaction is completed, diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain product Sub 1-14 (20g, 67%).

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

Synthesis of Sub 1-I-29

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

Synthesis of Sub 1-II-29

Sub 1-I-29 (27g, 68mmol), PPh ₃ (45g, 171mmol), and o -Dichlorobenzene (150mL) were added to a round bottom flask to obtain the product Sub 1-II- using the above synthesis method of Sub 1-II-1. 29 (22g, 92%) was obtained.

Synthesis of Sub 1-29

In a 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 (1.3g) 6.2mmol), NaO(t-Bu) (18g, 186mmol), and Toluene (300mL) were used to obtain the product Sub 1-29 (20g, 67%) using the synthesis method of Sub 1-1.

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

Synthesis of Sub 1-I-25

In a round bottom flask, 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) ), P(t-Bu) ₃ (3.1 g, 15.34 mmol), NaO(t-Bu) (44.32 g, 461.2 mmol), and Toluene (340 mL) using the synthesis method of Sub 1-I-1. The product Sub 1-I-25 (41.7 g, 73%) was obtained.

Synthesis of Sub 1-II-25

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

Synthesis of Sub 1-25

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) in a round bottom flask. , 10.4 mmol), NaO(t-Bu) (30.08 g, 313.045 mmol), and Toluene (230 mL) were used to obtain the product Sub 1-25 (34.77 g, 82%) using the synthesis method of Sub 1-1. .

Example of Sub 1

Meanwhile, the compounds belonging to Sub 1 may be the following compounds, but are not limited thereto, and Table 1 shows the FD-MS values of the compounds 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. Example of synthesis of Sub 2

Sub 2 of Scheme 1 can be synthesized through the reaction route of Scheme 3 below, but is not limited thereto.

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

Examples of synthesis of compounds belonging to Sub 2 of Scheme 3 are as follows.

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

Synthesis of Sub 2-I-1

In a round bottom flask, 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, it is heated and refluxed at 70°C for 4 hours. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain the product Sub 2-I-1 (99 g, 85%).

Synthesis of Sub 2-II-1

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

Synthesis of Sub 2-III-1

Add Sub 2-II-1 (70g, 293mmol), N-Bromosuccinimide (52g, 293mmol), and Methylene chloride (1L) to the round bottom flask. Then, stir at room temperature for 4 hours. When the reaction is complete, distilled water is added and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain the product Sub 2-III-1 (86 g, 83%).

Synthesis of Sub 2-1

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) in a round bottom flask. ), NaO(t-Bu) (24.6g, 255mmol), and Toluene (240mL) are added. Then, it is heated and refluxed at 110°C for 8 hours. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain product Sub 2-1 (28g, 76%).

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

Synthesis of Sub 2-2

In a 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), and Toluene (240mL) were used to produce the product Sub 2-2 (32g, 76%) using the synthesis method of Sub 2-1. ) was obtained.

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

Synthesis of Sub 2-3

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

Sub 2-37 Synthesis example (when a= 0, b=1, Y= O)

Synthesis of Sub 2-I-37

In a round bottom flask, 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 (43g, 74%) was obtained using H ₂ O (300 mL) using the above synthesis method for 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 a round bottom flask using the above synthesis method of Sub 2-II-1 to obtain the product Sub 2-II- 37 (23g, 82%) was obtained.

Synthesis of Sub 2-III-37

Sub 2-II-37 (23g, 89mmol), N-Bromosuccinimide (16g, 89mmol), and Methylene chloride (300mL) were added to a round bottom flask to obtain the product Sub 2-III- using the above synthesis method of Sub 2-III-1. 37 (21g, 70%) was obtained.

Synthesis of Sub 2-37

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) in a round bottom flask. mmol), NaO(t-Bu) (18g, 187mmol), and Toluene (200mL) were used to obtain the product Sub 2-37 (16g, 63%) using the synthesis method of Sub 2-1.

Synthesis example of Sub 2-144 (when 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) to obtain the product Sub 2-I-144 (47.72 g, 69%) using the Sub 2-I-1 synthesis method. got it

Synthesis of Sub 2-II-144

Sub 2-I-144 (47 g, 149 mmol), PPh ₃ (97.7 g, 372.48 mmol), and o -Dichlorobenzene (596 mL) were added to the round bottom flask to produce the product 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

Sub 2-II-144 (30g, 89mmol), N-Bromosuccinimide (18.8 g, 105.9 mmol), and methylene chloride (318 mL) were added to a round bottom flask to obtain product Sub 2 using the synthesis method of Sub 2-III-1. -III-144 (18.24 g, 53%) was obtained.

Synthesis of Sub 2-144

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) in a round bottom flask. g, 4.97 mmol), NaO(t-Bu) (14.4 g, 149.9 mmol), and Toluene (109 mL) to obtain the product Sub 2-144 (15.03 g, 69%) using the synthesis method of Sub 2-1 above. got it

Example of Sub 2

Meanwhile, the compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows the FD-MS values of the compounds 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)

Example of Sub 3

Meanwhile, the compounds belonging to Sub 3 may be the following compounds, but are not limited thereto, and Table 3 shows the FD-MS values of the compounds 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

Add Sub 1 or Sub 2 compound (1 equivalent) to a round bottom flask, Sub 3 compound (1 equivalent), Pd(PPh ₃ ) ₄ (0.03-0.05 equivalent), NaOH (3 equivalent), THF (3 mL / 1 mmol), add water (1.5 mL/1 mmol). Afterwards, it is heated and refluxed at 80℃. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with Toluene and Acetone to obtain the product.

Synthesis of Compound 1-2

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 in a round bottom flask. Add (30mL)/H ₂ O (15mL). Then, it is heated and refluxed at 80°C for 8 hours. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized with Toluene and Acetone to obtain product 1-2 (5.4 g, 80%).

Synthesis of compounds 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 used to obtain product 1-7 (11.3g, 85%) using the above synthesis method 1-2.

Synthesis of compounds 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 used to obtain product 1-14 (12.3g, 82%) using the above synthesis method 1-2.

Synthesis of compounds 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 used to obtain product 1-20 (12.5g, 83%) using the above synthesis method 1-2.

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)/ Product 1-26 (4.9g, 72%) was obtained using H ₂ O (15mL) using the above synthesis method 1-2.

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)/ Product 1-27 (6.5g, 85%) was obtained using H ₂ O (15mL) using the above synthesis method 1-2.

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 used to obtain product 1-33 (13.5g, 91%) using the above synthesis method 1-2.

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)/ Product 1-51 (3.5g, 51%) was obtained using H ₂ O (15mL) using the above synthesis method 1-2.

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)/ Product 1-52 (3.8g, 56%) was obtained using H ₂ O (15mL) using the above synthesis method 1-2.

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)/ Product 1-53 (4.2g, 62%) was obtained using H ₂ O (15mL) using the above synthesis method 1-2.

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 (20mL) was used to obtain product 1-66 (8.5g, 63%) using the above synthesis method 1-2.

Synthesis of compound 1-71

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 1-71 (4.7g, 73%) using the above synthesis method 1-2.

Synthesis of compound 1-78

In a 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), Product 1-78 (5.3g, 65%) was obtained using THF (40mL)/H ₂ O (20mL) using the synthesis method 1-2 above.

Synthesis of Compound 1-90

In a 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 ( Product 1-90 (5.8g, 48%) was obtained using synthesis method 1-2 above (40mL)/H ₂ O (20mL).

Synthesis of Compound 2-1

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 2-1 (5.5g, 81%) using the above synthesis method 1-2.

Synthesis of Compound 2-2

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 2-2 (6.1g, 80%) using the above synthesis method 1-2.

Synthesis of compounds 2-3

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 2-3 (5.8g, 76%) using the above synthesis method 1-2.

Synthesis of compounds 2-6

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) in a round bottom flask. )/H ₂ O (20mL) was used to obtain product 2-6 (10.3g, 81%) using synthesis method 1-2 above.

Synthesis of compounds 2-7

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) in a round bottom flask. )/H ₂ O (20mL) was used to obtain product 2-7 (11g, 74%) using the above synthesis method 1-2.

Synthesis of compounds 2-8

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) in a round bottom flask. )/H ₂ O (20mL) was used to obtain product 2-8 (12g, 81%) using synthesis method 1-2 above.

Synthesis of Compound 2-33

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 2-1 (5.0g, 82%) using the above synthesis method 1-2.

Synthesis of Compound 2-38

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 in a round bottom flask. (30mL)/H ₂ O (15mL) was used to obtain product 2-1 (4.4g, 74%) using the above synthesis method 1-2.

Synthesis of compound 2-133

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) in a round bottom flask. )/H ₂ O (15mL) was used to obtain product 2-133 (5.6g, 72%) using synthesis method 1-2 above.

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

<Scheme 4>

Sub 4 synthesis example

Sub 4 of Scheme 4 can be synthesized through the reaction route of Scheme 5 below, but is not limited thereto. (Hal ¹ is Br, Cl, I, and W, R ¹² , R ¹³ , R ¹⁴ , g, h, and i are as defined in Formula 2.)

<Scheme 5>

1. Sub 4-1 Synthesis Example

(1) Sub 4-c-1 synthesis

After dissolving 4-bromodibenzo[b,d]furan (50.0 g, 202 mmol) in toluene in a round bottom flask, 2-chloroaniline (25.8 g, 202 mmol), Pd ₂ (dba) ₃ (5.56 g, 6.07 mmol) , P( t -Bu) ₃ (2.46 g, 12.1 mmol), NaO t -Bu (38.9 g, 405 mmol) were added and stirred at 100°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the produced compound was recrystallized by applying a silica gel column to obtain 45.2 g of product (yield: 76%).

(2) Sub 4-1 synthesis

Sub 4-c-1 (45.2 g, 154 mmol) was added to DMA (mL), then Pd(OAc) ₂ (1.04 g, 4.61 mmol), K ₂ CO ₃ (63.8 g, 461 mmol), P(t -Bu) ₃ H·BF ₄ (g, 9.23 mmol) was added and stirred at 90°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the produced compound was recrystallized by applying a silica gel column to obtain 34.8 g of product (yield: 88%).

2. Sub 4-6 synthesis example

(1) Sub 4-a-6 synthesis

After dissolving 3-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in DMF (700 mL), bis(pinacolato)diboron (51.1 g, 201 mmol), KOAc (53.9 g, 549 mmol) ), PdCl ₂ (dppf) (4.02 g, 5.49 mmol) was added and stirred at 120 ^o C. When the reaction is complete, DMF is removed through distillation and extracted with CH ₂ Cl ₂ and water. When extraction is complete, the organic layer is dried with MgSO ₄ and concentrated. Afterwards, the produced compound was recrystallized by applying a silica gel column to obtain 46.3 g of product (yield: 79%).

(2) Sub 4-b-6 synthesis

Sub 4-a-6 (46.3 g, 145 mmol) obtained in the above synthesis was dissolved in THF (600 mL), then 1-bromo-2-nitrobenzene (29.2 g, 145 mmol), K ₂ CO ₃ (60.0 g, 434 mmol), Pd(PPh ₃ ) ₄ (5.01 g, 4.34 mmol), and water (300 mL) were added and stirred at 80 ^o C. When the reaction was completed, the extract was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Afterwards, the produced compound was recrystallized by applying a silica gel column to obtain 38.8 g of product (yield: 85%).

(3) Sub 4-6 synthesis

Sub 4-b-6 (38.8 g, 123 mmol) obtained in the above synthesis was dissolved in o -dichlorobenzene (700 mL), then triphenylphosphine (80.6 g, 307 mmol) was added and stirred at 200 ^o C. When the reaction was completed, o -dichlorobenzene was removed through distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried with MgSO ₄ and concentrated. Afterwards, the produced compound was recrystallized by applying a silica gel column to obtain 30.3 g of product (yield: 87%).

3. Sub 4-10 Synthesis Example

(1) Sub 4-a-10 synthesis

1-bromodibenzo[b,d]selenophene (50.0 g, 161 mmol), bis(pinacolato)diboron (45.0 g, 177 mmol), KOAc (47.5 g, 484 mmol), PdCl ₂ (dppf) (3.54 g, 4.84 mmol) ) was carried out in the same manner as the experimental method of Sub 4-a-6 above to obtain 41.5 g of product (yield: 72%).

(2) Sub 4-b-10 synthesis

Sub 4-a-10 (41.5 g, 116 mmol), 1-bromo-2-nitrobenzene (23.5 g, 116 mmol), K ₂ CO ₃ (18.14 g, 348 mmol), Pd(PPh ₃ ) ₄ obtained above. (8.05 g, 6.97 mmol) was performed in the same manner as in Sub 4-b-6 to obtain 34.4 g of product (yield: 84%).

(3) Sub 4-10 synthesis

Sub 4-b-10 (34.4 g, 97.5 mmol) and triphenylphosphine (64.0 g, 244 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 25.6 g of product (yield: 82%). .

4. Sub 4-12 Synthesis example

(1) Sub 4-a-12 synthesis

4-bromodibenzo[b,d]thiophene (50.0 g, 190 mmol), bis(pinacolato)diboron (53.1 g, 209 mmol), KOAc (55.9 g, 570 mmol), PdCl ₂ (dppf) (4.17 g, 5.70 mmol) ) was carried out in the same manner as the experimental method of Sub 4-a-6 above to obtain 42.4 g of product (yield: 72%).

(2) Sub 4-b-12 synthesis

Sub 4-a-12 (42.4 g, 137 mmol), 1-bromo-2-nitrobenzene (27.6 g, 137 mmol), K ₂ CO ₃ (56.7 g, 410 mmol), Pd(PPh ₃ ) ₄ obtained above. (9.49 g, 8.21 mmol) was processed in the same manner as in Sub 4-b-6 to obtain 33.8 g of product (yield: 81%).

(3) Sub 4-12 synthesis

Sub 4-b-12 (33.8 g, 111 mmol) and triphenylphosphine (72.7 g, 277 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 22.7 g of product (yield: 75%). .

5. Sub 4-13 Synthesis example

(1) Sub 4-c-13 synthesis

4-bromodibenzo[b,d]furan (50.0 g, 202 mmol), 1-chloronaphthalen-2-amine (35.9 g, 202 mmol), Pd ₂ (dba) ₃ (5.56 g, 6.07 mmol), P( t - Bu) ₃ (2.46 g, 12.1 mmol) and NaO t -Bu (38.9 g, 405 mmol) were used in the same manner as in Sub 4-c-1 to obtain 52.2 g of product (yield: 75%).

(2) Sub 4-13 synthesis

Sub 4-c-13 (52.2 g, 152 mmol), Pd(OAc) ₂ (1.02 g, 4.55 mmol), K ₂ CO ₃ (62.9 g, 455 mmol), P(t-Bu) ₃ H·BF ₄ (11.4 mL, 9.11 mmol) was carried out in the same manner as in Sub 4-1 to obtain 37.8 g of product (yield: 81%).

6. Sub 4-28 Synthesis example

(1) Sub 4-c-28 synthesis

6-bromodinaphtho[1,2-b:1',2'-d]thiophene (50.0 g, 138 mmol), 2-chloroaniline (17.6 g, 138 mmol), Pd ₂ (dba) ₃ (3.78 g, 4.13 mmol) ), P( t -Bu) ₃ (1.67 g, 8.26 mmol), and NaO t -Bu (26.5 g, 275 mmol) were used in the same manner as in Sub 4-c-1 to produce 88.0 g of product (yield: 78 %) was obtained.

(2) Sub 4-28 synthesis

Sub 4-c-28 (88.0 g, 215 mmol), Pd(OAc) ₂ (1.45 g, 6.44 mmol), K ₂ CO ₃ (89.0 g, 644 mmol), P(t-Bu) ₃ H·BF ₄ (16.1 mL, 12.9 mmol) was carried out in the same manner as in Sub 4-1 to obtain 69.0 g of product (yield: 86%).

7. Sub 4-38 Synthesis example

(1) Sub 4-c-38 synthesis

6-bromobenzo[b]naphtho[2,1-d]thiophene (50.0 g, 160 mmol), 2-chloroaniline (20.4 g, 160 mmol), Pd ₂ (dba) ₃ (4.39 g, 4.79 mmol), P( t -Bu) ₃ (1.94 g, 9.58 mmol) and NaO t -Bu (30.7 g, 319 mmol) were used in the same manner as in Sub 4-c-1 to obtain 41.4 g of product (yield: 72%). .

(2) Sub 4-38 synthesis

Sub 4-c-38 (41.4 g, 115 mmol), Pd(OAc) ₂ (0.774 g, 3.45 mmol), K ₂ CO ₃ (47.7 g, 345 mmol), P(t-Bu) ₃ H·BF ₄ (8.63 mL, 6.90 mmol) was carried out in the same manner as in Sub 4-1 to obtain 30.5 g of product (yield: 82%).

8. Sub 4-51 Synthesis example

(1) Sub 4-a-51 synthesis

3-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol), bis(pinacolato)diboron (51.1 g, 201 mmol), KOAc (53.9 g, 549 mmol), PdCl ₂ (dppf) (4.02 g, 5.49 mmol) was carried out in the same manner as the experimental method of Sub 4-a-6 to obtain 45.7 g of product (yield: 78%).

(2) Sub 4-b-51 synthesis

Sub 4-a-51 (45.7 g, 143 mmol), 2-bromo-3-nitronaphthalene (36.0 g, 143 mmol), K ₂ CO ₃ (59.2 g, 428 mmol), Pd(PPh ₃ ) ₄ obtained above. (9.90 g, 8.57 mmol) was performed in the same manner as in Sub 4-b-6 to obtain 43.3 g of product (yield: 83%).

(3) Sub 4-51 synthesis

Sub 4-b-51 (43.3 g, 118 mmol) and triphenylphosphine (77.7 g, 296 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 34.0 g of product (yield: 86%). .

9. Sub 4-68 Synthesis Example

(1) Sub 4-a-68 synthesis

3-bromo-5,5-dimethyl-5H-dibenzo[b,d]silole (50.0 g, 173 mmol), bis(pinacolato)diboron (48.3 g, 190 mmol), KOAc (50.9 g, 519 mmol), PdCl ₂ (dppf) (3.79 g, 5.19 mmol) was prepared in the same manner as in Sub 4-a-6 to obtain 45.9 g of product (yield: 79%).

(2) Sub 4-b-68 synthesis

Sub 4-a-68 (45.9 g, 137 mmol), 2-bromo-3-nitronaphthalene (34.4 g, 137 mmol), K ₂ CO ₃ (56.6 g, 410 mmol), Pd(PPh ₃ ) ₄ obtained above. (9.47 g, 8.19 mmol) was carried out in the same manner as in Sub 4-b-6 to obtain 43.2 g of product (yield: 83%).

(3) Sub 4-68 synthesis

Sub 4-b-68 (43.2 g, 113 mmol) and triphenylphosphine (74.3 g, 283 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 33.7 g of product (yield: 85%). .

10. Sub 4-81 Synthesis example

(1) Sub 4-a-81 synthesis

1-bromodibenzo[b,d]furan (50.0 g, 202 mmol), bis(pinacolato)diboron (56.5 g, 223 mmol), KOAc (59.6 g, 607 mmol), PdCl ₂ (dppf) (4.44 g, 6.07 mmol) ) was carried out in the same manner as the experimental method of Sub 4-a-6 above to obtain 44.0 g of product (yield: 74%).

(2) Sub 4-b-81 synthesis

Sub 4-a-81 (44.0 g, 150 mmol), 1-bromo-2-nitronaphthalene (37.7 g, 150 mmol), K ₂ CO ₃ (62.1 g, 449 mmol), Pd(PPh ₃ ) ₄ obtained above. (10.4 g, 8.98 mmol) was carried out in the same manner as in Sub 4-b-6 to obtain 39.6 g of product (yield: 78%).

(3) Sub 4-81 synthesis

Sub 4-b-81 (39.6 g, 117 mmol) and triphenylphosphine (76.6 g, 292 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 31.2 g of product (yield: 87%). .

11. Sub 4-94 Synthesis Example

(1) Sub 4-a-94 synthesis

6-bromobenzo[b]naphtho[2,1-d]thiophene (50.0 g, 160 mmol), bis(pinacolato)diboron (44.6 g, 176 mmol), KOAc (47.0 g, 479 mmol), PdCl ₂ (dppf) (3.50 g, 4.79 mmol) was carried out in the same manner as the experimental method of Sub 4-a-6 above to obtain 40.3 g of product (yield: 70%).

(2) Sub 4-b-94 synthesis

Sub 4-a-94 (40.3 g, 112 mmol), 1-bromo-2-nitrobenzene (22.6 g, 112 mmol), K ₂ CO ₃ (46.3 g, 335 mmol), Pd(PPh ₃ ) ₄ obtained above. (7.75 g, 6.70 mmol) was carried out in the same manner as in the experimental method of Sub 4-b-6 to obtain 33.0 g of product (yield: 83%).

(3) Sub 4-94 synthesis

Sub 4-b-94 (33.0 g, 92.7 mmol) and triphenylphosphine (60.8 g, 232 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 24.0 g of product (yield: 80%). .

12. Sub 4-110 Synthesis Example

(1) Sub 4-a-110 synthesis

8-bromobenzo[b]naphtho[1,2-d]selenophene (50.0 g, 139 mmol), bis(pinacolato)diboron (38.8 g, 153 mmol), KOAc (40.9 g, 417 mmol), PdCl ₂ (dppf) (3.05 g, 4.17 mmol) was carried out in the same manner as the experimental method of Sub 4-a-6 above to obtain 40.7 g of product (yield: 72%).

(2) Sub 4-b-110 synthesis

Sub 4-a-110 (40.7 g, 100 mmol), 1-bromo-2-nitrobenzene (20.2 g, 100 mmol), K ₂ CO ₃ (41.5 g, 300 mmol), Pd(PPh ₃ ) ₄ obtained above. (6.93 g, 6.00 mmol) was performed in the same manner as in Sub 4-b-6 to obtain 33.8 g of product (yield: 84%).

(3) Sub 4-110 synthesis

Sub 4-b-110 (33.8 g, 84.0 mmol) and triphenylphosphine (55.2 g, 210 mmol) obtained above were subjected to the same experimental method as Sub 4-6 to obtain 27.4 g of product (yield: 88%). .

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

compound FD-MS compound FD-MS Sub4-1 m/z=257.08(C ₁₈ H ₁₁ NO=257.29) Sub4-2 m/z=273.06(C ₁₈ H ₁₁ NS=273.35) Sub4-3 m/z=405.15(C ₃₁ H ₁₉ N=405.50) Sub4-4 m/z=299.11(C ₂₀ H ₁₇ NSi=299.45) Sub4-5 m/z=257.08(C ₁₈ H ₁₁ NO=257.29) Sub4-6 m/z=283.14(C ₂₁ H ₁₇ N=283.37) Sub4-7 m/z=273.06(C ₁₈ H ₁₁ NS=273.35) Sub4-8 m/z=299.11(C ₂₀ H ₁₇ NSi=299.45) Sub4-9 m/z=407.17(C ₃₁ H ₂₁ N=407.52) Sub4-10 m/z=321.01(C ₁₈ H ₁₁ NSe=320.25) Sub4-11 m/z=257.08(C ₁₈ H ₁₁ NO=257.29) Sub4-12 m/z=273.06(C ₁₈ H ₁₁ NS=273.35) Sub4-13 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-14 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-15 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-16 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-17 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-18 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-19 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-20 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-21 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-22 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-23 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-24 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-25 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-26 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-27 m/z=399.14(C ₂₈ H ₂₁ NSi=399.57) Sub4-28 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-29 m/z=383.17(C ₂₉ H ₂₁ N=383.49) Sub4-30 m/z=357.12(C ₂₆ H ₁₅ NO=357.41) Sub4-31 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-32 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-33 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-34 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-35 m/z=455.17(C ₃₅ H ₂₁ N=455.56) Sub4-36 m/z=371.02(C ₂₂ H ₁₃ NSe=370.31) Sub4-37 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-38 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-39 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-40 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-41 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-42 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-43 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-44 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-45 m/z=357.12(C ₂₆ H ₁₅ NO=357.41) Sub4-46 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-47 m/z=407.13(C ₃₀ H ₁₇ NO=407.47) Sub4-48 m/z=423.11(C ₃₀ H ₁₇ NS=423.53) Sub4-49 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-50 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-51 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-52 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-53 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-54 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-55 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-56 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-57 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-58 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-59 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-60 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-61 m/z=357.12(C ₂₆ H ₁₅ NO=357.41) Sub4-62 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-63 m/z=357.12(C ₂₆ H ₁₅ NO=357.41) Sub4-64 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-65 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-66 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-67 m/z=457.18(C ₃₅ H ₂₃ N=457.58) Sub4-68 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-69 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-70 m/z=473.16(C ₃₄ H ₂₃ NSi=473.65) Sub4-71 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-72 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-73 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-74 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-75 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-76 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-77 m/z=483.17(C ₂₉ H ₂₁ N=383.49) Sub4-78 m/z=399.14(C ₂₈ H ₂₁ NSi=399.57) Sub4-79 m/z=507.20(C ₃₉ H ₂₅ N=507.64) Sub4-80 m/z=523.18(C ₃₈ H ₂₅ NSi=523.71) Sub4-81 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-82 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-83 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-84 m/z=471.14(C ₃₄ H ₂₁ NSi=471.63) Sub4-85 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-86 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-87 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-88 m/z=371.02(C ₂₂ H ₁₃ NSe=370.31) Sub4-89 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-90 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-91 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-92 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-93 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-94 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-95 m/z=383.17(C ₂₉ H ₂₁ N=383.49) Sub4-96 m/z=421.04(C ₂₆ H ₁₅ NSe=420.37) Sub4-97 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-98 m/z=357.12(C ₂₆ H ₁₅ NO=357.41) Sub4-99 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-100 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-101 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-102 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-103 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-104 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-105 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-106 m/z=349.13(C ₂₄ H ₁₉ NSi=349.51) Sub4-107 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-108 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-109 m/z=333.15(C ₂₅ H ₁₉ N=333.43) Sub4-110 m/z=371.02(C ₂₂ H ₁₃ NSe=370.31) Sub4-111 m/z=307.10(C ₂₂ H ₁₃ NO=307.35) Sub4-112 m/z=323.08(C ₂₂ H ₁₃ NS=323.41) Sub4-113 m/z=383.17(C ₂₉ H ₂₁ N=383.49) Sub4-114 m/z=399.14(C ₂₈ H ₂₁ NSi=399.57) Sub4-115 m/z=373.09(C ₂₆ H ₁₅ NS=373.47) Sub4-116 m/z=357.12(C ₂₆ H ₁₅ NO=357.41)

Example of Sub 5

An example of Sub 5 of Scheme 4 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub5-1 m/z=240.05(C ₁₄ H ₉ ClN ₂ =240.69) Sub5-2 m/z=290.06(C ₁₈ H ₁₁ ClN ₂ =290.75) Sub5-3 m/z=290.06(C ₁₈ H ₁₁ ClN ₂ =290.75) Sub5-4 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-5 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-6 m/z=316.08(C ₂₀ H ₁₃ ClN ₂ =316.79) Sub5-7 m/z=316.08(C ₂₀ H ₁₃ ClN ₂ =316.79) Sub5-8 m/z=392.11(C ₂₆ H ₁₇ ClN ₂ =392.89) Sub5-9 m/z=241.04(C ₁₃ H ₈ ClN ₃ =241.68) Sub5-10 m/z=241.04(C ₁₃ H ₈ ClN ₃ =241.68) Sub5-11 m/z=241.04(C ₁₃ H ₈ ClN ₃ =241.68) Sub5-12 m/z=242.04(C ₁₂ H ₇ ClN ₄ =242.67) Sub5-13 m/z=242.04(C ₁₂ H ₇ ClN ₄ =242.67) Sub5-14 m/z=395.09(C ₂₃ H ₁₄ ClN ₅ =395.09) Sub5-15 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-16 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-17 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-18 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-19 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-20 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-21 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-22 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-23 m/z=405.10(C ₂₆ H ₁₆ ClN ₃ =405.89) Sub5-24 m/z=405.10(C ₂₆ H ₁₆ ClN ₃ =405.89) Sub5-25 m/z=405.10(C ₂₆ H ₁₆ ClN ₃ =405.89) Sub5-26 m/z=405.10(C ₂₆ H ₁₆ ClN ₃ =405.89) Sub5-27 m/z=356.11(C ₂₃ H ₁₇ ClN ₂ =356.85) Sub5-28 m/z=356.11(C ₂₃ H ₁₇ ClN ₂ =356.85) Sub5-29 m/z=356.11(C ₂₃ H ₁₇ ClN ₂ =356.85) Sub5-30 m/z=356.11(C ₂₃ H ₁₇ ClN ₂ =356.85) Sub5-31 m/z=480.14(C ₃₃ H ₂₁ ClN ₂ =481.00) Sub5-32 m/z=480.14(C ₃₃ H ₂₁ ClN ₂ =481.00) Sub5-33 m/z=480.14(C ₃₃ H ₂₁ ClN ₂ =481.00) Sub5-34 m/z=360.03(C ₂₀ H ₁₃ BrN ₂ =361.24) Sub5-35 m/z=360.03(C ₂₀ H ₁₃ BrN ₂ =361.24) Sub5-36 m/z=410.04(C ₂₄ H ₁₅ BrN ₂ =411.30) Sub5-37 m/z=410.04(C ₂₄ H ₁₅ BrN ₂ =411.30) Sub5-38 m/z=466.01(C ₂₆ H ₁₅ BrN ₂ S=467.38) Sub5-39 m/z=290.06(C ₁₈ H ₁₁ ClN ₂ =290.75) Sub5-40 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-41 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-42 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-43 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-44 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-45 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-46 m/z=442.12(C ₃₀ H ₁₉ ClN ₂ =442.95) Sub5-47 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-48 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-49 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-50 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-51 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-52 m/z=445.11(C ₂₇ H ₁₆ ClN ₅ =455.91) Sub5-53 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-54 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-55 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-56 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-57 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-58 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-59 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-60 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-61 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-62 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-63 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-64 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-65 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-66 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-67 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-68 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-69 m/z=290.06(C ₁₈ H ₁₁ ClN ₂ =290.75) Sub5-70 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-71 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-72 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-73 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-74 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-75 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-76 m/z=442.12(C ₃₀ H ₁₉ ClN ₂ =442.95) Sub5-77 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-78 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-79 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-80 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-81 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-82 m/z=445.11(C ₂₇ H ₁₆ ClN ₅ =455.91) Sub5-83 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-84 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-85 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-86 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-87 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-88 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-89 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-90 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-91 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-92 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-93 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-94 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-95 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-96 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-97 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-98 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-99 m/z=290.06(C ₁₈ H ₁₁ ClN ₂ =290.75) Sub5-100 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-101 m/z=340.08(C ₂₂ H ₁₃ ClN ₂ =340.81) Sub5-102 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-103 m/z=390.09(C ₂₆ H ₁₅ ClN ₂ =390.87) Sub5-104 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-105 m/z=366.09(C ₂₄ H ₁₅ ClN ₂ =366.85) Sub5-106 m/z=442.12(C ₃₀ H ₁₉ ClN ₂ =442.95) Sub5-107 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-108 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-109 m/z=291.06(C ₁₇ H ₁₀ ClN ₃ =291.74) Sub5-110 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-111 m/z=292.05(C ₁₆ H ₉ ClN ₄ =292.73) Sub5-112 m/z=445.11(C ₂₇ H ₁₆ ClN ₅ =455.91) Sub5-113 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-114 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-115 m/z=396.05(C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub5-116 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-117 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-118 m/z=380.07(C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub5-119 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-120 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-121 m/z=455.12(C ₃₀ H ₁₈ ClN ₃ =455.95) Sub5-122 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-123 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-124 m/z=406.12(C ₂₇ H ₁₉ ClN ₂ =406.91) Sub5-125 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-126 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-127 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-128 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-129 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-130 m/z=346.03(C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub5-131 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-132 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-133 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-134 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-135 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-136 m/z=330.06(C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub5-137 m/z=245.08(C ₁₄ H ₄ D ₅ ClN ₂ =245.72) Sub5-138 m/z=295.09(C ₁₈ H ₆ D ₅ ClN ₂ =295.78) Sub5-139 m/z=295.09(C ₁₈ H ₆ D ₅ ClN ₂ =295.78)

Synthesis example of Final products 2

After dissolving Sub 4 (1 equivalent) in toluene in a round bottom flask, Sub 5 (1.1 equivalent), Pd ₂ (dba) ₃ (0.03 equivalent), P( t -Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalents) was added and stirred at 100°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain final product 2.

1. 3-1 Synthesis example

Sub 4-1 (34.8 g, 135 mmol), Toluene (500 mL), Sub 5-1 (32.6 g, 135 mmol), Pd ₂ (dba) ₃ (3.72 g, 4.06 mmol), P( t -Bu) ₃ (1.64 g, 8.12 mmol) and NaO t -Bu (26.0 g, 271 mmol) were added and stirred at 100°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 48.7 g of product (yield: 78%).

2. 3-6 Synthesis example

Sub 4-6 (30.3 g, 107 mmol), Sub 5-39 (31.1 g, 107 mmol), Pd ₂ (dba) ₃ (2.94 g, 3.21 mmol), P( t -Bu) ₃ (1.30 g, 6.42 mmol), NaO t -Bu (20.6 g, 214 mmol) was used to obtain 42.0 g of the final product (yield: 73%) using the synthesis method in 3-1 above.

3. 3-10 Synthesis example

Sub 4-10 (25.6 g, 79.9 mmol), Sub 5-99 (23.2 g, 79.9 mmol), Pd ₂ (dba) ₃ (2.20 g, 2.40 mmol), P( t -Bu) ₃ (0.97 g, 4.80 mmol), NaO t -Bu (15.4 g, 160 mmol) was used to obtain 34.9 g of the final product (yield: 76%) using the synthesis method in 3-1 above.

4. 3-12 Synthesis example

Sub 4-12 (22.7 g, 83.0 mmol), Sub 5-7 (26.3 g, 83.0 mmol), Pd ₂ (dba) ₃ (2.28 g, 2.49 mmol), P( t -Bu) ₃ (1.01 g, 4.98 mmol), NaO t -Bu (16.0 g, 166 mmol) was used to obtain 37.7 g of the final product (yield: 82%) using the synthesis method in 3-1 above.

5. 3-13 Synthesis example

Sub 4-13 (37.8 g, 123 mmol), Sub 5-17 (42.7 g, 123 mmol), Pd ₂ (dba) ₃ (3.38 g, 3.69 mmol), P( t -Bu) ₃ (1.49 g, 7.38 mmol), NaO t -Bu (23.6 g, 246 mmol) was used to obtain 57.0 g of the final product (yield: 75%) using the synthesis method in 3-1.

6. 3-28 Synthesis example

Sub 4-28 (69.0 g, 185 mmol), Sub 5-1 (44.5 g, 185 mmol), Pd ₂ (dba) ₃ (5.08 g, 5.54 mmol), P( t -Bu) ₃ (2.24 g, 11.1 mmol), NaO t -Bu (35.5 g, 370 mmol) was used to obtain 76.8 g of the final product (yield: 72%) using the synthesis method in 3-1 above.

7. 3-38 Synthesis example

Sub 4-38 (30.5 g, 94.3 mmol), Sub 5-35 (34.1 g, 94.3 mmol), Pd ₂ (dba) ₃ (2.59 g, 2.83 mmol), P( t -Bu) ₃ (1.14 g, 5.66 mmol), NaO t -Bu (18.1 g, 189 mmol) was used to obtain 41.0 g of the final product (yield: 72%) using the synthesis method in 3-1 above.

8. 3-51 Synthesis example

Sub 4-51 (34.0 g, 102 mmol), Sub 5-3 (29.6 g, 102 mmol), Pd ₂ (dba) ₃ (2.80 g, 3.06 mmol), P( t -Bu) ₃ (1.24 g, 6.12 mmol), NaO t -Bu (19.6 g, 204 mmol) was used to obtain 42.6 g of the final product (yield: 71%) using the synthesis method in 3-1 above.

9. 3-68 Synthesis example

Sub 4-68 (33.7 g, 96.4 mmol), Sub 5-126 (33.4 g, 96.4 mmol), Pd ₂ (dba) ₃ (2.65 g, 2.89 mmol), P( t -Bu) ₃ (1.17 g, 5.79 mmol), NaO t -Bu (18.5 g, 193 mmol) was used to obtain 42.6 g of the final product (yield: 67%) using the synthesis method in 3-1 above.

10. 3-81 Synthesis example

Sub 4-81 (31.2 g, 102 mmol), Sub 5-99 (29.5 g, 102 mmol), Pd ₂ (dba) ₃ (2.79 g, 3.05 mmol), P( t -Bu) ₃ (1.23 g, 6.09 mmol), NaO t -Bu (19.5 g, 203 mmol) was used to obtain 42.2 g of the final product (yield: 74%) using the synthesis method in 3-1 above.

11. 3-94 Synthesis example

Sub 4-94 (24.0 g, 74.2 mmol), Sub 5-13 (18.0 g, 74.2 mmol), Pd ₂ (dba) ₃ (2.04 g, 2.23 mmol), P( t -Bu) ₃ (0.901 g, 4.45 mmol), NaO t -Bu (14.3 g, 148 mmol) was used to obtain 30.3 g of the final product (yield: 77%) using the synthesis method in 3-1 above.

12. 3-110 Synthesis example

Sub 4-110 (27.4 g, 74.0 mmol), Sub 5-15 (25.7 g, 74.0 mmol), Pd ₂ (dba) ₃ (2.03 g, 2.22 mmol), P( t -Bu) ₃ (8.98 g, 4.44 mmol), NaO t -Bu (14.2 g, 14.8 mmol) was used to obtain 35.3 g of the final product (yield: 70%) using the synthesis method in 3-1 above.

compound FD-MS compound FD-MS 3-1 m/z=461.15(C ₃₂ H ₁₉ N ₃ O=461.52) 3-2 m/z=477.13(C ₃₂ H ₁₉ N ₃ S=477.59) 3-3 m/z=659.24(C ₄₉ H ₂₉ N ₃ =659.79) 3-4 m/z=503.18(C ₃₄ H ₂₅ N ₃ Si=503.68) 3-5 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-6 m/z=537.22(C ₃₉ H ₂₇ N ₃ =537.67) 3-7 m/z=477.13(C ₃₂ H ₁₉ N ₃ S=477.59) 3-8 m/z=553.20(C ₃₈ H ₂₇ N ₃ Si=553.74) 3-9 m/z=661.25(C ₄₉ H ₃₁ N ₃ =661.81) 3-10 m/z=575.09(C ₃₆ H ₂₁ N ₃ Se=574.55) 3-11 m/z=537.18(C ₃₈ H ₂₃ N ₃ O=537.62) 3-12 m/z=553.16(C ₃₈ H ₂₃ N ₃ S=553.68) 3-13 m/z=617.16(C ₄₂ H ₂₃ N ₃ OS=617.73) 3-14 m/z=527.15(C ₃₆ H ₂₁ N ₃ S=527.65) 3-15 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-16 m/z=603.21(C ₄₂ H ₂₉ N ₃ Si=603.80) 3-17 m/z=643.21(C ₄₅ H ₂₉ N ₃ S=543.81) 3-18 m/z=629.23(C ₄₄ H ₃₁ N ₃ Si=629.84) 3-19 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-20 m/z=527.15(C ₃₆ H ₂₁ N ₃ S=527.65) 3-21 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-22 m/z=603.18(C ₄₂ H ₂₅ N ₃ S=603.74) 3-23 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-24 m/z=603.21(C ₄₂ H ₂₉ N ₃ Si=603.80) 3-25 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-26 m/z=667.17(C ₄₆ H ₂₅ N ₃ OS=667.79) 3-27 m/z=679.24(C ₄₈ H ₃₃ N ₃ Si=679.90) 3-28 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-29 m/z=663.27(C ₄₉ H ₃₃ N ₃ =663.82) 3-30 m/z=637.22(C ₄₆ H ₂₇ N ₃ O=637.74) 3-31 m/z=627.23(C ₄₅ H ₂₉ N ₃ O=627.75) 3-32 m/z=527.15(C ₃₆ H ₂₁ N ₃ S=527.65) 3-33 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-34 m/z=553.20(C ₃₈ H ₂₇ N ₃ Si=553.74) 3-35 m/z=735.27(C ₅₅ H ₃₃ N ₃ =735.89) 3-36 m/z=625.11(C ₄₀ H ₂₃ N ₃ Se=624.61) 3-37 m/z=611.20(C ₄₄ H ₂₅ N ₃ O=611.70) 3-38 m/z=603.18(C ₄₂ H ₂₅ N ₃ S=603.74) 3-39 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-40 m/z=627.18(C ₄₄ H ₂₅ N ₃ S=627.77) 3-41 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-42 m/z=692.20(C ₄₈ H ₂₈ N ₄ S=692.84) 3-43 m/z=613.25(C ₄₅ H ₃₁ N ₃ =613.76) 3-44 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-45 m/z=637.22(C ₄₆ H ₂₇ N ₃ O=637.74) 3-46 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-47 m/z=767.20(C ₅₄ H ₂₉ N ₃ OS=767.91) 3-48 m/z=727.21(C ₅₂ H ₂₉ N ₃ S=727.89) 3-49 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-50 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-51 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-52 m/z=703.24(C ₅₀ H ₃₃ N ₃ Si=703.92) 3-53 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-54 m/z=633.13(C ₄₂ H ₂₃ N ₃ S ₂ =633.79) 3-55 m/z=587.20(C ₄₂ H ₂₅ N ₃ O=587.68) 3-56 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-57 m/z=613.25(C ₄₅ H ₃₁ N ₃ =613.76) 3-58 m/z=768.27(C ₅₄ H ₃₆ N ₄ Si=769.00) 3-59 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-60 m/z=527.15(C ₃₆ H ₂₁ N ₃ S=527.65) 3-61 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-62 m/z=667.17(C ₄₆ H ₂₅ N ₃ OS=667.79) 3-63 m/z=611.20(C ₄₄ H ₂₅ N ₃ O=611.70) 3-64 m/z=627.18(C ₄₄ H ₂₅ N ₃ S=627.77) 3-65 m/z=587.20(C ₄₂ H ₂₅ N ₃ O=587.68) 3-66 m/z=709.16(C ₄₈ H ₂₇ N ₃ S ₂ =709.89) 3-67 m/z=661.25(C ₄₉ H ₃₁ N ₃ =661.81) 3-68 m/z=659.19(C ₄₄ H ₂₉ N ₃ SSi=659.88) 3-69 m/z=613.25(C ₄₅ H ₃₁ N ₃ =613.76) 3-70 m/z=677.23(C ₄₈ H ₃₁ N ₃ Si=677.88) 3-71 m/z=601.18(C ₄₂ H ₂₃ N ₃ O ₂ =601.67) 3-72 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-73 m/z=537.22(C ₃₉ H ₂₇ N ₃ =537.67) 3-74 m/z=659.19(C ₄₄ H ₂₉ N ₃ SSi=659.88) 3-75 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-76 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-77 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-78 m/z=604.21(C ₄₁ H ₂₈ N ₃ Si=604.79) 3-79 m/z=711.27(C ₅₃ H ₃₃ N ₃ =711.87) 3-80 m/z=727.24(C ₅₂ H ₃₃ N ₃ Si=727.94) 3-81 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-82 m/z=527.15(C ₃₆ H ₂₁ N ₃ S=527.65) 3-83 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-84 m/z=725.23(C ₅₂ H ₃₁ N ₃ Si=725.93) 3-85 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-86 m/z=633.13(C ₄₂ H ₂₃ N ₃ S ₂ =633.79) 3-87 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-88 m/z=625.11(C ₄₀ H ₂₃ N ₃ Se=624.61) 3-89 m/z=611.20(C ₄₄ H ₂₅ N ₃ O=611.70) 3-90 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-91 m/z=537.22(C ₃₉ H ₂₇ N ₃ =537.67) 3-92 m/z=629.23(C ₄₄ H ₃₁ N ₃ Si=629.84) 3-93 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-94 m/z=529.14(C ₃₄ H ₁₉ N ₅ S=529.62) 3-95 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-96 m/z=676.12(C ₄₃ H ₂₄ N ₃ Se=675.65) 3-97 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-98 m/z=563.17(C ₃₈ H ₂₁ N ₅ O=563.62) 3-99 m/z=561.18(C ₄₀ H ₂₃ N ₃ O=561.64) 3-100 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-101 m/z=537.22(C ₃₉ H ₂₇ N ₃ =537.67) 3-102 m/z=705.26(C ₅₀ H ₃₅ N ₃ Si=705.94) 3-103 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-104 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-105 m/z=537.22(C ₃₉ H ₂₇ N ₃ =537.67) 3-106 m/z=603.21(C ₄₂ H ₂₉ N ₃ Si=603.80) 3-107 m/z=587.20(C ₄₂ H ₂₅ N ₃ O=587.68) 3-108 m/z=682.19(C ₄₅ H ₂₆ N ₆ S=682.81) 3-109 m/z=613.25(C ₄₅ H ₃₁ N ₃ =613.76) 3-110 m/z=681.08(C ₄₂ H ₂₃ N ₃ SSe=680.69) 3-111 m/z=511.17(C ₃₆ H ₂₁ N ₃ O=511.58) 3-112 m/z=577.16(C ₄₀ H ₂₃ N ₃ S=577.71) 3-113 m/z=587.24(C ₄₃ H ₂₉ N ₃ =587.73) 3-114 m/z=653.23(C ₄₆ H ₃₁ N ₃ Si=653.86) 3-115 m/z=632.21(C ₄₄ H ₂₀ D ₅ N ₃ S=632.80) 3-116 m/z=566.22(C ₄₀ H ₁₈ D ₅ N ₃ O=566.67)

Manufacturing evaluation of organic electric devices

Example 1) Fabrication and testing 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 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 60 nm thick film. Next, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was added to a thickness of 60 nm. A hole transport layer was formed by vacuum deposition. A 50:50 mixture of the invention compounds represented by Formula (1) and Formula (2) was used as a host on the top of the hole transport layer, and (piq) ₂ Ir(acac) [bis-(1-) was used as a dopant. A 30 nm thick light emitting layer was deposited on the hole transport layer by doping [phenylisoquinolyl)iridium(Ⅲ)acetylacetonate] at a weight ratio of 95:5. (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinoline oleato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm as a hole-blocking layer, and the electron transport layer Tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Afterwards, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode to manufacture an organic electroluminescent device.

[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 Formula 1 was used solely as a host.

[Comparative Examples 4 to 7]

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Formula 2 was used solely 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 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 Formula 2 and Comparative Compound 1 were used as a mixture.

A forward bias direct current voltage was applied to the organic electroluminescent devices of Examples and Comparative Examples manufactured in this way, and the electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch. As a result of the measurement, the electroluminescence (EL) characteristics were measured at a standard luminance of 2500 cd/m2. T95 lifespan was measured using a lifespan measuring device manufactured by McScience. The table below shows the results of device fabrication and evaluation.

first host 2nd host 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 (3-5) - 4.3 14.5 2500 17.3 103.2 Comparative example (5) Compound (3-12) - 4.5 15.2 2500 16.4 86.3 Comparative example (6) Compound (3-28) - 4.2 13.2 2500 19.0 108.7 Comparative example (7) Compound (3-39) - 4.2 14.0 2500 17.9 92.3 Comparative example (8) Compound (2-133) Comparative compound 1 4.3 12.6 2500 19.8 105.3 Comparative example (9) Compound (3-12) Comparative compound 2 4.1 9.6 2500 26.1 112.8 Comparative example (10) Compound (3-12) Comparative compound 3 4.2 10.6 2500 23.5 108.1 Example (1) Compound (1-56) Compound (3-5) 4.0 6.7 2500 37.3 150.1 Example (2) Compound (2-43) Compound (3-5) 4.0 6.5 2500 38.2 151.6 Example (3) Compound (2-133) Compound (3-5) 3.8 6.2 2500 40.1 154.3 Example (4) Compound (1-56) Compound (3-12) 4.1 7.2 2500 34.6 121.1 Example (5) Compound (2-43) Compound (3-12) 4.1 7.1 2500 35.1 122.6 Example (6) Compound (2-133) Compound (3-12) 3.9 6.1 2500 41.1 124.3 Example (7) Compound (1-56) Compound (3-28) 3.9 6.5 2500 38.7 152.8 Example (8) Compound (2-43) Compound (3-28) 3.9 6.4 2500 39.2 153.3 Example (9) Compound (2-133) Compound (3-28) 3.7 6.2 2500 40.4 155.4 Example (10) Compound (1-56) Compound (3-39) 3.9 6.5 2500 38.5 129.1 Example (11) Compound (2-43) Compound (3-39) 3.8 6.5 2500 38.7 129.5 Example (12) Compound (2-133) Compound (3-39) 3.7 6.3 2500 39.6 130.4

As can be seen from the results in Table 8 above, when the materials for the organic electroluminescent device of the present invention represented by Formula 1 and Formula 2 are mixed and used as a phosphorescent host (Examples 1 to 12), a device using a single material (Comparative Example) It was confirmed that the driving voltage, efficiency and lifespan were significantly improved compared to the device (Comparative Examples 8 to 10) using a mixture of 1 to 7) and comparative compounds.

In other words, Comparative Examples 8 to 10 in which Comparative Compound 1 or Comparative Compound 2 were mixed and used as a phosphorescent host compared to the case where the compounds of the present invention represented by Formula 1 and Formula 2 were used alone as phosphorescent hosts (Comparative Examples 1 to 7). The results were generally excellent in terms of efficiency and lifespan, and Examples 1 to 12, which mixed the compounds of the present invention represented by Formula 1 and Formula 2, showed significantly superior effects in terms of driving voltage, efficiency, and lifespan. Able to know.

Based on the above experimental results, the present inventors determined that a mixture of a substance of Formula 1 and a substance of Formula 2 has new properties other than those of each substance, and that 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, it was confirmed that when the compounds of the present invention, Chemical Formula 1 and Chemical Formula 2, were mixed, a new PL wavelength was formed, unlike when they were used alone, and the decrease and extinction time of the newly formed PL wavelength was similar to that of the Chemical Formula 1 and Chemical Formula 2 materials, respectively. It was confirmed that the decrease and extinction times increased. This means that when the compounds of the present invention are mixed and used, not only do electrons and holes move through the energy levels of each material, but also electrons and holes move or energy due to a new region (exciplex) with a new energy level formed by mixing. It is believed that efficiency and lifespan increase through delivery. As a result, this can be said to be an important example in which the mixed thin film exhibits exciplex energy transfer and light emission processes when using the mixture of the present invention.

In addition, the reason why the combination of the present invention is superior to Comparative Examples 8 to 10, which were used as phosphorescent hosts mixed with comparative compounds, is that the polycyclic ring compound represented by Formula 2 has characteristics such as stability against not only electrons but also holes, and high T1. When mixing a compound represented by Formula 1 with strong hole characteristics, the electron blocking ability is improved due to the high T1 and high LUMO energy value, and more holes move quickly and easily to the light emitting layer. As a result, the charge balance between holes and electrons within the light-emitting layer increases, allowing light to be emitted from within the light-emitting layer rather than at the hole transport layer interface. As a result, deterioration at the HTL interface is also reduced, thereby maximizing the driving voltage, efficiency, and lifespan of the entire device. . In other words, it is believed that the combination of Chemical Formula 1 and Chemical Formula 2 acts synergistically electrochemically to improve the overall performance of the device.

first host 2nd host mixing ratio
(1st host
: 2nd host) Voltage Current
Density Brightness
(cd/m2) Efficiency Lifetime
T(95) Example (13) compound
(1-56) compound
(3-5) 2:8 3.6 7.0 2500 35.6 148.3 Example (14) compound
(1-56) compound
(3-5) 3:7 3.8 6.9 2500 36.1 148.8 Example (15) compound
(1-56) compound
(3-5) 4:6 3.9 6.8 2500 36.8 149.5 Example (16) compound
(2-133) compound
(3-28) 2:8 3.4 6.5 2500 38.4 150.1 Example (17) compound
(2-133) compound
(3-28) 3:7 3.5 6.4 2500 38.9 153.6 Example (18) compound
(2-133) compound
(3-28) 4:6 3.7 6.4 2500 39.1 154.2

As shown in Table 9 above, devices were manufactured and measured using a mixture of compounds of the present invention in different ratios (2:8, 3:7, 4:6).

To explain the results in detail, it was confirmed that the driving voltage result improved as the second host ratio increased, but the opposite trend was observed in terms of efficiency and lifespan. Therefore, in the case of mixtures, since the amount of mixing ratio affects the characteristics, it is judged to be a very important task to derive a mixing ratio that maximizes the charge balance in the light-emitting layer.

The above description is merely an illustrative description of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are for illustrative purposes rather than limiting 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 in accordance with the claims below, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

100: organic electric device 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 (16)

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

{In the above formulas (1) and (2),
1) W, 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 selected from the group consisting of hydrogen; C ₁ ~ C ₅₀ alkyl group; and C ₆ ~ C ₆₀ aryl group; or R' and R" form a ring with each other to form a spy Forms 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;
5) Ar ¹ and Ar ² are each independently hydrogen; heavy hydrogen; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; is selected from the group consisting of,
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; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; and C ₂ to C ₂₀ alkenyl group; is selected from the group consisting of,

When l, m, n, o and ^p are 2 or more, each ^is a ^plurality and is the same or different from each other and is adjacent to ^each other. ⁵ groups and a plurality of R ⁶ groups can combine with each other to form aromatic and heteroaromatic rings,
8) R ¹² , R ¹³ and R ¹⁴ are each independently hydrogen; heavy hydrogen; halogen; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₁ ~ C ₅₀ alkyl group; And C ₂ ~ C ₂₀ alkenyl group; selected from the group consisting of,
When g, h and i are 2 or more, they are each plural, the same or different from each other, and a plurality of adjacent R ^12s , a plurality of R ^13s , and a plurality of R ^14s can combine with each other to form aromatic and heteroaromatic rings,
9) n, l, p and q are any integer from 0 to 4, m is 0 or 1, o is any integer from 0 to 3,
10) g and i are any integer from 0 to 4, h is any integer from 0 to 2,
11) Two adjacent * in the formula (2) combine with * in the formula (2-1) to form a ring,
Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, alkyl group, and alkenyl group each contain deuterium; halogen; Cyano group; nitro group; C ₁ -C ₂₀ alkoxyl group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; and C ₂ -C ₂₀ heterocyclic group; It may be further substituted with one or more substituents selected from the group consisting of.}
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} above formulas ( ³ ) ^{and ( 4} ), Same as defined in claim 1 above.) The organic electric device according to claim 1, wherein the compound represented by 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} above formulas ( ⁵ ) ^{to ( 12} ), Same as defined in claim 1 above.) The organic electric device according to claim 1, wherein l, m, n, o and p are all 0. According to claim 1, wherein any one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an organic electric device characterized in that a pair of neighboring bonds to each other to form a ring. The organic electric device of claim 1, wherein X or Y is S or O. The organic electric device according to claim 1, wherein the formula (1) is any one of the following compounds:
























































The organic electric device according to claim 1, wherein the compound represented by the formula (2) includes a compound represented by any one of the following formulas (13) to (17).
Formula (13) Formula (14) Formula (15) Formula (16) Formula (17)

(In the above formulas (13) to (17), Ar ² , L ² , R ⁶ , g, h, i, q, R' and R" are as defined in claim 1,
R ^12' , R ^13' and R ^14' are the same as the definitions of R ¹² , R ¹³ and R ¹⁴ in claim 1 above.)
The organic electric device according to claim 1, wherein the compound represented by the formula (2) includes a compound represented by any one of the following formulas (18) to (63).
Formula (18) Formula (19) Formula (20) Formula (21)

Formula (22) Formula (23) Formula (24) Formula (25)

Formula (26) Formula (27) Formula (28) Formula (29)

Formula (30) Formula (31) Formula (32) Formula (33)

Formula (34) Formula (35) Formula (36) Formula (37)

Formula (38) Formula (39) Formula (40) Formula (41)

Formula (42) Formula (43) Formula (44) Formula (45)

Formula (46) Formula (47) Formula (48) Formula (49)

Formula (50) Formula (51) Formula (52) Formula (53)

Formula (54) Formula (55) Formula (56) Formula (57)

Formula (58) Formula (59) Formula (60) Formula (61)

Formula (62) Formula (63)

(In the above formulas (18) to (63), Ar ² , L ² , R ⁶ , g, h, i, q and W are as defined in claim 1,
R ^12' , R ^13' and R ^14' are the same as the definitions of R ¹² , R ¹³ and R ¹⁴ in claim 1 above,
t is any integer from 0 to 4, and s and u are each independently any integer from 0 to 6.)
The organic electric device according to claim 1, wherein R ⁶ in the formula (2) is hydrogen. The organic electric device according to claim 1, wherein the formula (2) is one of the following compounds:




























The organic electric device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in any one of a weight ratio of 1:9 to 9:1. The organic electric device according to claim 1, wherein the compounds represented by Formula (1) and Formula (2) are mixed at a weight ratio of 1:9 to 5:5. The organic electric device according to claim 1, wherein the compounds represented by Formula (1) and Formula (2) are mixed at a weight ratio of 2:8 to 3:7. An electronic device comprising: a display device comprising the organic electric element according to claim 1; and a control unit driving the display device. The electronic device according to claim 15, wherein the organic electric 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.