KR101512058B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The invention displays compounds indicated by chemical equation 1. In addition, it displays organic electronic device that includes, electrode 1, 2 and an organic matter layer between them. The abovementioned organic matter layer includes compounds indicated by chemical equation 1. If the organic matter layer includes compounds indicated by chemical equation 1, it can improve the radiation efficiency, the stability and the lifetime.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption becomes a very important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases. As the driving voltage decreases, the crystallization of the organic material due to Joule heating, which occurs during driving, Indicating a tendency for the lifetime to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimum combination of the energy level and the T ₁ value between the respective organic layers, and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time.

In order to lower the driving voltage, a hole mobility material was developed. In order to increase the hole mobility, the packing density was high and the HOMO value was greatly different from the HOMO value of the light emitting layer However, the efficiency is decreased in the case of a material having a high hole mobility.

This is because the hole mobility is faster than the electron mobility in a general organic electronic device, resulting in charge unbalance in the light emitting layer, resulting in reduction in luminous efficiency and lifetime.

When the charge mobility in the light emitting layer is controlled by reducing the hole mobility using a material having a relatively low packing density, the driving voltage is increased due to the low packing density, and thus the joule heat is increased and the device lifetime is reduced. Therefore, it is urgently required to develop a material having a high packing density and excellent hole trapping ability.

It is an object of the present invention to provide a compound capable of improving luminous efficiency, stability and lifetime of a device, an organic electric device using the same, and an electronic device therefor.

In one aspect, the invention provides compounds represented by the formula:

In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.

By using the compound according to the embodiment of the present invention, the luminous efficiency, stability and lifetime of the device can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected." In addition, when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, And the like. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

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

The term " halo "or" halogen ", as used herein, unless otherwise specified, refers to fluorine (F), bromine (Br), chlorine (Cl), or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

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

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

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

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spiroid fluorene group, or the like.

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

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

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed by bonding to each other.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Neighboring functional groups may be formed by bonding to each other.

As used herein, the term "heteroatom" refers to N, O, S, P or Si, etc., unless otherwise stated.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

In addition, a no explicit description, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro _{group, C 1 -C 20, C 1} -C _20, an alkoxyl group of, C ₁ -C ₂₀ alkyl amine group, C ₁ -C ₂₀ alkyl thiophene group, C ₆ -C ₂₀ aryl thiophene group, C ₂ -C ₂₀ alkenyl, C ₂ -C of ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron Group, a germanium group, and a C ₂ -C ₂₀ heterocyclic group, and the substituent is not limited to these substituents.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

1 is an illustration of an organic electroluminescent device according to an embodiment of the present invention.

1, an organic electroluminescent device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 formed on a substrate 110, And an organic material layer containing a compound according to the present invention is provided between the two electrodes 180. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers other than the light emitting layer 150 and the hole transporting layer 140 may not be formed. The electron blocking layer may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, etc., and the electron transporting layer 160 may serve as a hole blocking layer.

Further, although not shown, the organic electroluminescent device according to an embodiment of the present invention further includes a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer can do.

The compound according to one embodiment of the present invention applied to the organic material layer includes a hole injecting layer 130, a hole injecting layer 140, an electron transporting layer 160, an electron injecting layer 170, a light emitting layer 150, 151) or a light-efficiency-improvement layer or the like. For example, the compound of the present invention may be used in at least one of the hole transport layer 140, the hole injection layer 130, the light emitting layer 150, and the light emitting auxiliary layer 151.

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like may be different depending on which substituent is bonded at which position, even if the same mother nucleus is used, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T ₁ value between the organic layers, and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life 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 various deposition methods. For example, a metal or a metal oxide having conductivity or an alloy thereof may be deposited on a substrate to form a cathode 120, and a hole injection layer 130, An organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 may be deposited, and then a material usable as a cathode 180 may be deposited thereon.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

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

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or a device for monochromatic or white illumination.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by the following formula (1).

≪ Formula 1 >

Wherein Ar ^a is represented by the following general formula (2), Ar ^b is represented by the following general formula (3), Ar ^c is a C ₆ -C ₆₀ aryl group, a fluorenyl group, a C ₂ -C ₆₀ heterocyclic group , And a C ₁ -C ₆₀ alkyl group. Wherein the heterocyclic group comprises at least one heteroatom selected from the group consisting of O, N, S, Si and P, Ar ^c is phenyl, biphenyl, naphthyl, substituted or unsubstituted fluorene, dibenzothi Dibenzofuran, carbazole, and the like.

 &Lt; Formula 2 > < EMI ID =

,

,

In the general formulas (2) and (3), m and n are independently an integer of 0 or 1. For example, both m and n may be 0 or 1, n = 0 or 1 when m = 0, and m = 0 or 1 when n = 0. At this time, it is preferable that n is also 1 when m = 1. For example, when an X ² containing ring is formed, it is preferable that an X ¹ containing ring is also formed.

In Formula 2 and 3, X ¹ and X ² are independently of each other, NR 'O, S, or CR'R "may be one where, R' and R" are independently of one another, C ₆ -C ₆₀ An aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; And a C ₁ -C ₆₀ alkyl group. For example, R 'and R "are each independently of the other phenyl, biphenyl, naphthyl, dibenzothiophene, 9,9-dimethylfluorene, quinazoline, pyrimidine, deuterium substituted phenyl, , Naphthyl substituted with phenyl, methyl, spirofluorene, and the like.

In the general formulas (2) and (3), L ₁ and L ₂ independently represent a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; C ₂ -C _{60 divalent} heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And a divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring.

In the general formulas (2) and (3), 1 is an integer of 0 to 4, o and p are each an integer of 0 to 3, q is an integer of 0 to 6, and R ¹ to R ⁴ are each independently selected from the group consisting of deuterium; Tritium; A halogen group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; An alkyl group having _{1 to 60} carbon atoms; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₃ -C ₆₀ cycloalkyl group; A C ₁ -C ₃₀ alkoxy group; A C ₆ -C ₃₀ aryloxy group; And ^{-L 3 -N (R 5) (} R 6); may be selected from the group consisting of.

Meanwhile, adjacent groups of R ¹ to R ⁴ may combine with each other to form at least one ring. Here, R ¹ to R ⁴ which do not form a ring may be respectively defined as defined above. For example, when l and o are both 2, adjacent R ^{1 s} may combine with each other to form a ring, and R ² may be an aryl group or a heterocyclic group independently of each other even when adjacent to each other. Of course, when l is an integer of 2 or more, a plurality of R &lt; ^{1 &gt; s} may be the same or different, and a group in which some of the adjacent groups are bonded to each other to form a ring and not form a remaining ring is selected from the above- . The same applies when o, p, or q is an integer of 2 or more.

The rings formed by the adjacent groups include at least one heteroatom selected from the group consisting of C ₃ -C ₆₀ aliphatic rings, C ₆ -C ₆₀ aromatic rings, O, N, S, Si and P A fused ring consisting of a C ₂ -C ₆₀ hetero ring, or a combination thereof, and may be a single ring or multiple rings, as well as a saturated or unsaturated ring.

L ³ independently represents a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; C ₂ -C _{60 divalent} heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And a divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring.

R ⁵ and R ⁶ are independently of each other a C ₆ -C ₆₀ aryl group; A fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a C ₁ -C ₆₀ alkyl group; for example, phenyl, biphenyl, naphthyl, phenyl substituted with naphthyl, and the like.

The R ⁵ and R ⁶ , L ³ (excluding single bond), R ⁵ or L ³ (excluding single bond) and R ⁶ are bonded to each other to form a heterocyclic compound containing N together with N bonded thereto It is possible.

When each of the symbols is an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxyl group, an aryloxyl group, an arylene group and a fluorenylene group, Respectively; deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ An aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And -L ³ -N (R ⁵ ) (R ⁶ );

Illustratively, the formula (2) may be represented by one of the following formulas.

 &Lt; Formula 4 > < EMI ID =

In the general formulas (4) to (7), each symbol such as R ', R ", R ³ , R ⁴ , L ¹ , p and q may be defined as defined in formula (2).

Illustratively, the formula (3) may be represented by one of the following formulas.

 &Lt; Formula 8 > < EMI ID =

In the above Formulas 8 to 11, symbols such as R ', R ", R ¹ , R ² , L ² , 1, and o may be defined as defined in Formula 3.

In the above Chemical Formulas 2 to 11, at least one of R ¹ to R ⁴ may include deuterium.

More specifically, the compound represented by Formula 1 may be one of the following compounds.

In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer may include a compound represented by Formula 1, wherein the organic compound layer includes a hole injection layer, a hole transport layer, And may be contained in at least one layer of the luminescent auxiliary layer or the luminescent layer. That is, the compound represented by the formula (1) can be used as a material for the hole injection layer, the hole transport layer, the light emission assisting layer or the light emitting layer.

Specifically, the organic layer includes an organic electroluminescent device including the compound represented by the above-mentioned individual formulas P1-1 to P1-40, P2-1 to P2-30, P3-1 to P3-30, and P4-1 to P4-30 Lt; / RTI &gt;

In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.

On the other hand, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1). For example, the hole transport layer of the organic layer according to an embodiment of the present invention may contain two different compounds such as the individual compounds P1-1 and P1-2, and the individual compounds P1-1, P2-1 and P3- Lt; RTI ID = 0.0 &gt; 1. &Lt; / RTI &gt;

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Illustratively, the compound according to the present invention may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, or by reacting Sub 3 and Sub 4 as shown in Scheme 2 below.

<Reaction Scheme 1>

<Reaction Scheme 2>

I. Starting material Synthetic example

1. Synthesis of S-1 and S-3

<Reaction Scheme 3>

(1) Synthesis of S-1-I

(7.99 g, 6.91 mmol), Pd (PPh ₃ ) ₄ (35.9 g, 152.1 mmol), 1,3-dibromobenzene ₂ CO ₃ (57.3 g, 414.8 mmol) was added, dissolved in 608 mL of anhydrous THF and 304 mL of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by silicagel column and recrystallization to obtain 34.5 g (76%) of S-1-I.

(2) S-1, S- 3 of  synthesis

After dissolving the S-1-I (34.5 g, 105.1 mmol) and PPh ₃ (68.94 g, 263 mmol) in o-dichlorobenzene and refluxing for 24 hours, the solvent was removed by distillation under reduced pressure, The obtained product was separated by silicagel column and recrystallization. S-1 (11.8 g, 38%) and S-3 (14.3 g, 46%) were obtained respectively.

2. Synthesis of S-2

<Reaction Scheme 4>

(1) S-1- II Synthesis of

(8-nitronaphthalen-1-yl ) boronic acid (30g, 138.3mmol) and 1,4-dibromobenzene (35.9g, 152.1mmol) , Pd (PPh 3) 4 (7.99g, 6.91mmol), K 2 CO 3 ( 57.3 g, 414.8 mmol), THF 608 mL, and water 304 mL were treated in the same manner as in S-1-I to give 35.4 g (78%) of S-1-II.

(2) S- 2 of  synthesis

S-1-II (35.4 g, 107.9 mmol) and PPh ₃ (70.74 g, 269.7 mmol) were treated with 442 mL of o-dichlorobenzene in the same manner as in S-1 to obtain 25.2 g (79%) of S- .

3. Synthesis of S-4 and S-6

<Reaction Scheme 5>

(1) Synthesis of S-4-I

To a round bottom flask (3-bromophenyl) boronic acid ( 40g, 199.2mmol), (8-iodonaphthalen-1-yl) (methyl) sulfane (89.7g, 298.8mmol), Pd (PPh 3) 4 (11.5g, 9.96 mmol), K ₂ CO ₃ 876 mL of THF and 438 mL of water were treated in the same manner as in S-1-I to obtain 49.2 g (75%) of S-4-I.

(2) S-4- II Synthesis of

Dissolve S-5-I (49.2 g, 149.4 mmol), V ₂ O ₅ (2.7 g, 14.9 mmol) and 750 mL acetonitrile solution in a nitrogen-atmosphere round-bottomed flask and then dissolve in an ice bath The temperature was lowered to 0 ° C, H ₂ O ₂ aqueous solution (20.9 mL, 224 mmol, 33%) was added, and the mixture was stirred at 10 ° C. for 1 hour. When the reaction is complete, add 1 L of water to the reaction and dilute. After slowly raising the temperature to room temperature, it is extracted with 1.5 L of ethyl acetate. The obtained organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated to obtain 43.8 g (85%) of the resulting product.

(3) Synthesis of S-4 and S-6

H ₂ SO ₄ (132 mL) is added to the round bottom flask, and the temperature is lowered to 0 ° C to 5 ° C. S-4-II (43.8 g, 126.9 mmol) is slowly added dropwise. It is then stirred at 25 [deg.] C for 2 hours. After completion of the reaction, 1270 mL of cold water is slowly added, and the pH of the reaction solution is adjusted to pH 8 with K ₂ CO ₃ aqueous solution. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with anhydrous MgSO 4 and filtered under reduced pressure. S-4 (13.11 g, 35%) and S-6 (16.11, 43%) were obtained by separating the resulting product by silicagel column and recrystallization.

4. Synthesis of S-5

<Reaction Scheme 6>

(1) Synthesis of S-5-I

To a round bottom flask was added 4-bromophenyl boronic acid (40 g, 199.2 mmol), (8-iodonaphthalen-1-yl) (methyl) sulfane (89.7 g, 298.8 mmol), Pd (PPh ₃ ) ₄ mmol), K ₂ CO ₃ (82.6 g, 597.5 mmol), THF 876 mL, and water 438 mL were treated in the same manner as in S-1-I to give 50.5 g (77%) of S-5-I.

(2) S-5- II Synthesis of

S-5-I (50.5 g, 153.4 mmol), V ₂ O ₅ (2.8 g, 15.3 mmol), acetonitrile 770 mL and H ₂ O ₂ (21.5 g, 230 mmol) To obtain 41.8 g (79%) of S-5-II.

(3) Synthesis of S-5

S-5-II (41.8 g, 121.1 mmol) and H ₂ SO ₄ (126 mL) were treated in the same manner as in S-4 to obtain 27.7 g (73%) of S-5.

5. Synthesis of S-8

<Reaction Scheme 7>

(1) Synthesis of S-8-1

4-bromo-2-fluoro-1-iodobenzene (43.5 g, 144.6 mmol) and Pd (PPh ₃ ) ₄ (6.69 g, 115.7 mmol) were added to a round bottom flask. , 27.8 g (69%) of S-8-I was obtained by proceeding in the same manner as in S-1-I, except that K ₂ CO ₃ (48 g, 347.2 mmol), 510 mL of THF and 255 mL of water were used.

(2) Synthesis of S-8-2

S-8-1 (27.6 g, 79.9 mmol) and anhydrous CH ₂ Cl _{2 (} 229 mL) were added to a round bottom flask and cooled to 0 ° C. BBr ₃ was then added (25.1 g, 100 mmol), slowly raised to room temperature and stirred for 24 h. When the reaction is completed, the reaction mixture is cooled to -78 ° C., 300 mL of methanol is slowly added dropwise to the reaction mixture, and sufficient water is added again to inactivate the reaction mixture. After the reaction mixture was cooled to room temperature, the reaction mixture was extracted with CH ₂ Cl ₂ , and a small amount of water remaining in the organic layer was removed with anhydrous MgSO _{4. The} organic solvent was concentrated under reduced pressure, and the resulting product was separated by silicagel column and recrystallization. 24.8 g (97%) of S-8-2 was obtained.

(3) Synthesis of S-8

S-8-2 (24.8 g, 78.2 mmol), anhydrous N-methyl-2-pyrrolidinone (337 mL) and K ₂ CO ₃ (21.6 g, 156.4 mmol) were placed in a round bottom flask, Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, 2 L of toluene was added, and the mixture was stirred for 10 minutes. The solution was extracted with the solution and water. The solution was then removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by silicagel column and recrystallization to obtain 16 g of S-8 (69%).

6. Synthesis of S-10 and S-12

<Reaction Scheme 8>

(1) Synthesis of S-10-I

The starting material, 1-bromo-3-iodobenzene ( 55g, 194.4mmol), (8- (methoxycarbonyl) naphthalen-1-yl) boronic acid (53.7g, 233.3mmol), Pd (PPh 3) 4 (11.2g, 9.72 mmol), K ₂ CO ₃ (80.6 g, 583.2 mmol), THF (856 mL) and water (428 mL) were treated in the same manner as in S-1-I to give 50.4 g (76%) of S-10-1.

(2) S-10- II , S-12- II Synthesis of

S-10-I (50.4 g, 147.7 mmol) obtained in the above synthesis and 479.4 mL of methanesulfonic acid were dissolved in a round-bottomed flask and stirred at 50 ° C to 60 ° C. After completion of the reaction, the reaction mixture was cooled to 0 ° C and water was added thereto. The solid precipitate was filtered and washed with a small amount of water. CH ₂ dried over MgSO ₄ to melt back into the Cl ₂ and concentrated, then the resulting compound silicagel column and the product was recrystallized S-10 II-a (16g, 35%) and S-12-II (21.5g, 47%) .

(3) S-10- III Synthesis of

S-10-II (16 g, 51.75 mmol) obtained in the above synthesis was dissolved in 320 mL of ethylene glycol, and then hydrazine monohydrate (77.7 g, 1552.5 mmol) and KOH (7.3 g, 129.4 mmol) were added to a round bottom flask Lt; 0 &gt; C. When the reaction was completed, the temperature was lowered to 0 &lt; 0 &gt; C, water was added, and the precipitated solid was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 14.5 g (95%) of the product S-10-III.

(4) S-12- III Synthesis of

S-12-II (21.5 g) was treated in the same manner as in the synthesis of S-10-III to obtain 19 g (97%) of S-12-III.

(5) Synthesis of S-10

(14.5 g, 49.12 mmol), KOt-Bu (16.5 g, 147.36 mmol) and DMF (320 mL) were added to the round bottom flask, and the mixture was stirred at 0 ° C for 5 minutes. 20.9 g, 147.36 mmol). After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 14.4 g (91%) of the product S-10.

(6) Synthesis of S-12

S-12-III (19 g, 64.4 mmol) was treated in the same manner as in the synthesis of S-10 to obtain 18.7 g (90%) of S-12.

7. Synthesis of S-15

<Reaction Scheme 9>

(1) Synthesis of S-15-1

2-iodo-1,1'-biphenyl (19.5 g, 69.54 mmol) was added to a round bottom flask, and 230 mL of anhydrous THF was added under nitrogen atmosphere. The mixture was cooled to -78 ° C. and 30.5 mL Was slowly dropped. After 30 minutes, the above S-12-II (21.5 g, 69.54 mmol) was dissolved in 100 mL of anhydrous THF, and the mixture was slowly added dropwise, followed by stirring at room temperature. After completion of the reaction, 250 mL of water was added to complete the reaction. The reaction mixture was extracted with CH ₂ Cl _{2. The} obtained organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 24.5 g (76%) of the product.

(2) Synthesis of S-15

S-15-1 (24.5 g, 52.87 mmol) obtained above was placed in a round-bottomed flask, and 190 mL of acetic acid was added, and HCl (5.4 mL) was added and stirred under reflux. When the reaction was completed, the reaction mixture was cooled to room temperature, and 270 mL of water was added thereto. When a solid was formed, the mixture was filtered and washed with water. After nokhin the resulting solid with CH ₂ Cl ₂ and extracted with water and CH ₂ Cl _2. The resulting organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 18.4 g (78%) of the product.

On the other hand, the compounds belonging to the starting materials may be as follows, but the present invention is not limited thereto. Table 1 below shows FD-MS values of the compounds belonging to the starting materials.

[Table 1]

II . Sub  1 of Synthetic example

One. Sub  Synthesis of 1-1

<Reaction formula 10>

(One) Sub  Synthesis of 1-1 '

To a round bottom flask was added S-3 (40g, 135.1mmol) , iodobenzene (30.3g, 148.6mmol), Pd 2 (dba) 3 (6.2g, 6.75mmol), P (t-Bu) 3 (2.732g, 13.5mmol ), NaO t- Bu (38.96 g, 405.2 mmol) and toluene (1420 mL) were added thereto, followed by reaction at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 39.2 g (78%) of product Sub 1-1 '.

(2) Sbu  Synthesis of 1-2 '

Sub 1-1 '(39.2 g, 105.3 mmol) obtained in the above synthesis and 370 mL of anhydrous ether were placed in a round-bottomed flask, and the temperature of the reaction product was lowered to -78 ° C. and n-BuLi (2.5 M in hexane) mL, 115.8 mmol) was slowly added dropwise, and then the reaction was stirred for 30 minutes. The temperature of the reaction was then lowered to -78 ° C and triisopropyl borate (36.4 mL, 158 mmol) was added dropwise. The temperature is gradually raised, stirred at room temperature, diluted by adding water, and 2N HCl is added and stirred. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 24.1 g (68%) of Sub 1-2 '.

(3) Sub  Synthesis of 1-1

Sub 1-2 '(24.1g 71. 5mmol) obtained in the above synthesis in a round bottom flask, 1,4-dibromobenzene (25.3g, 107.2mmol ), Pd (PPh 3) 4 (4.13g, 3.57mmol), K 2 CO ₃ (29.6 g, 214.4 mmol), THF (314 mL) and water (157 mL), and the mixture is refluxed with stirring. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 23.4 g (73%) of Sub 1-1.

2. Sub  Synthesis of 1-7

<Reaction Scheme 11>

(One) Sub  Synthesis of 7-1 '

P (t-Bu) ₃ (2.4 g, 5.9 mmol), Pd ₂ (dba) ₃ (5.41 g, 5.9 mmol), 3-iododibenzo [b, d] thiophene (40.3 g, 130 mmol) , NaO t- Bu (34.1 g, 354.5 mmol) and 1240 mL of toluene were synthesized in the same manner as Sub 1-1 'to obtain 43 g (76%) of the product Sub 7-1'.

(2) Sub  Synthesis of 7-2 '

Sub 1-2 '(43 g, 89.9 mmol), anhydrous ether 315 mL, n-BuLi (2.5 M in hexane) (39.5 mL, 98.9 mmol) and triisopropyl borate (31.1 mL, 134.8 mmol) (69%) of the product Sub 7-2 'was obtained.

(3) Sub  Synthesis of 1-7

Sub 7-2 '(27.5g 62.0mmol), 4'-bromo-3-iodo-1,1'-biphenyl (33.4g, 93.0mmol), Pd (PPh 3) 4 (3.59g, 3.1mmol), K ₂ CO ₃ (25.7 g, 186 mmol), THF 272 mL, and water 136 mL were synthesized in the same manner as Sub 1-1 above to give 28.9 g (74%) of the product Sub 1-7.

3. Sub  Synthesis of 1-39

<Reaction Scheme 12>

(One) Sub  Synthesis of 39-1 '

S-8 (43 g, 185.1 mmol), anhydrous ether 650 mL, n-BuLi (2.5 M in hexane) (81.4 mL, 203.6 mmol) and triisopropyl borate (64.1 mL, 277.68 mmol) The synthesis proceeded to obtain 32 g (66%) of the product Sub 39-1 '.

(2) Sub  Synthesis of 1-39

Sub 39-1 '(32g, 122.1mmol) , 1,3,5-tribromobenzene (57.7g, 183.2mmol), Pd (PPh 3) 4 (7.06g, 6.1mmol), K 2 CO 3 (50.6g, 366.3 mmol), THF (536 mL), and water (268 mL) were synthesized in the same manner as Sub 1-1 above to give 42 g (76%) of the product Sub 1-39.

4. Sub  Synthesis of 1-42

<Reaction Scheme 13>

(One) Sub  Synthesis of 42-1 '

S-5 (50 g, 159.6 mmol), anhydrous ether 558 mL, n-BuLi (2.5 M in hexane) (70.2 mL, 175.6 mmol) and triisopropyl borate (55.3 mL, 239.5 mmol) The synthesis proceeded to obtain 28 g (64%) of the product Sub 42-1 '.

(2) Sub  Synthesis of 1-42

Sub 42-1 '(28g, 100.7mmol) , 2,7-dibromo-9,9-dimethyl-9H-fluorene (53.2g, 151mmol), Pd (PPh 3) 4 (5.82g, 5.03mmol), K 2 CO ₃ (41.7 g, 302 mmol), THF 442 mL, and water 221 mL were synthesized in the same manner as Sub 1-1 above to give 36.6 g (72%) of the product Sub 1-42.

5. Sub  Synthesis of 1-52

<Reaction Scheme 14>

(One) Sub  Synthesis of 52-1 '

S-12 (50 g, 154.7 mmol), anhydrous Ether 541 mL, n-BuLi (2.5 M in hexane) (68.1 mL, 170.2 mmol) and triisopropyl borate (53.5 mL, 232 mmol) To obtain 29 g (65%) of the product Sub 52-1 '.

(2) Sub  Synthesis of 1-52

Sub 52-1 '(29g, 100.6mmol) , 3,3'-dibromo-1,1'-biphenyl (47.1g, 151mmol), Pd (PPh 3) 4 (5.82g, 5.03mmol), K 2 CO 3 (41.7 g, 302 mmol), THF 442 mL, and water 221 mL were subjected to synthesis in the same manner as in Sub 1 to obtain 36.8 g (77%) of the product Sub 1-52.

6. Sub  Synthesis of 1-54

<Reaction Scheme 15>

(One) Sub  Synthesis of 54-1 '

Synthesis of S-17 (40 g, 89.8 mmol), anhydrous ether 314 mL, n-BuLi (2.5 M in hexane) (39.5 mL, 98.8 mmol) and triisopropyl borate (31.1 mL, To obtain 23.2 g (63%) of the product Sub 54-1 '.

(2) Sub  Synthesis of 1-54

Sub 54-1 '(23.2g, 56.5mmol) , 4'-bromo-3-iodo-1,1'-biphenyl (30.5g, 84.8mmol), Pd (PPh 3) 4 (3.3g, 2.83mmol), K ₂ CO ₃ (23.4 g, 169.6 mmol), THF 248 mL, and water 124 mL were synthesized in the same manner as Sub 1 to obtain 25 g (74%) of Sub 1-54.

On the other hand, compounds belonging to Sub 1 may be as follows, but are not limited thereto, and Table 2 shows FD-MS values of Sub 1 compounds.

[Table 2]

III . Sub  2 of Synthetic example

<Reaction Scheme 16>

One. Sub  2-1 Synthetic example

<Reaction Scheme 17>

Dibenzo [b, d] thiophen-3-amine (25 g, 125.5 mmol) and Pd ₂ (dba) ₃ (5.74 g, 6.3 mmol) were added to a round bottom flask. mmol), the process proceeds to _{P (t-Bu) 3 (} 2.54g, 12.5mmol), NaO t -Bu (36.2g, 376.4mmol), toluene reaction at 100 ℃ after loading a 1320mL. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried with MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 34 g (77%) of product Sub 2-1.

2. Sub  2-6 Synthetic example

<Reaction Scheme 18>

Dibenzo [b, d] furan-3-amine (25 g, 136.5 mmol), Pd ₂ (dba) ₃ (6.25 g, 6.82 mmol), P _{t-Bu) 3 (2.76g,} 13.65mmol), NaO t -Bu (39.3g, 409.4mmol), and the product 2-6 Sub proceeds to 1430mL toluene in the same manner as in the Sub 2-1 35.3g (74% ).

3. Sub  2-10 Synthetic example

<Reaction Scheme 19>

9-bromobenzo [b] naphtho [ 1,2-d] thiophene (72.9g, 233mmol), 4-aminobenzonitrile (25g, 211.6mmol), Pd 2 (dba) 3 (9.7g, 10.6mmol), P (t- Bu) ₃ (4.28 g, 21.2 mmol), NaO t- Bu (61.01 g, 634.8 mmol) and toluene 2220 mL were treated in the same manner as Sub 2-1 to obtain 51.9 g (70%) of product Sub 2-10 .

4. Sub  2-25 Synthetic example

<Reaction Scheme 20>

1-bromonaphthalene (36.7g, 177.2mmol) , aniline (15g, 161.1mmol), Pd 2 (dba) 3 (7.37g, 8.05mmol), P (t-Bu) 3 (3.26g, 16.1mmol), NaO t -Bu (46.4 g, 483.2 mmol) and 1690 mL of toluene were carried out in the same manner as Sub 2-1 to obtain 27.2 g (77%) of the product Sub 2-25.

5. Sub  2-43 Synthetic example

<Reaction Scheme 21>

(52.7 g, 97.5 mmol), [1,1'-biphenyl] -4-amine (52.7 g, 97.5 mmol) was added to a solution of 7-bromo-9,9-dimethyl-N, N-di (naphthalen- (15g, 88.6mmol), with _{Pd 2 (dba) 3 (4.1g} , 4.43mmol), P (t-Bu) 3 (1.8g, 8.9mmol), NaO t -Bu (25.6g, 266mmol), toluene 930mL Proceeding in the same manner as Sub 2-1, 39.6 g (71%) of the product Sub 2-43 was obtained.

On the other hand, compounds belonging to Sub 2 may be as follows, but the present invention is not limited thereto, and Table 3 shows FD-MS values of compounds belonging to Sub 2.

[Table 3]

IV . The final product ( Final Products )of Synthetic example

1. Final product Synthetic example  One: ( Sub  1 of 2 Coupled  rescue)

Sub 1 (1.1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), P (t-Bu) ₃ (0.1 eq.), NaO t -Bu (3 eq.), toluene (10.5 mL / Sub 2 1 mmol), and the mixture was stirred at 100 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain the final product.

2. Final product Synthetic example  2: (same Sub  2 Coupled  rescue)

(1.2 eq.), Sub 1 (1 eq.), Pd ₂ (dba) ₃ (0.1 eq.), P (t-Bu) ₃ (0.2 eq.), NaO t -Bu (6.6 eq.), toluene (6 mL / Sub 2 1 mmol), and the mixture was stirred at 100 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain the final product

3. Final product Synthetic example  3: (different Sub  2 Coupled  rescue)

(1 eq.), Sub 1 (1.1 eq.), Pd ₂ (dba) ₃ (0.06 eq.), P (t-Bu) ₃ (0.12 eq.), NaO t- toluene (10.5 mL / Sub 2 1 mmol), and the mixture was stirred at 100 ° C. After the reaction is complete, the reaction mixture is extracted with CH ₂ Cl ₂ and water. The organic layer is dried over MgSO ₄ and concentrated. The resulting compound is recrystallized from a silicagel column. It was placed in the reaction (1.1 eq) obtained round bottom flask another Sub 2 (1 _{eq), Pd 2 (dba) 3} (0.05 eq.), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 Equivalent), and toluene (10.5 mL / sub 2 mmol). When the reaction was completed, the product was obtained using the above method.

(One) P1 Synthesis of -1

<Reaction Formula 22>

P (t-Bu) ₃ (0.86 g, 4.3 mmol), Sub 2-1 (15 g, 42.7 mmol), Sub 1-1 (21 g, 46.9 mmol), Pd ₂ (dba) ₃ (1.95 g, 2.13 mmol) , NaO t- Bu (12.3 g, 128 mmol) and 448 mL of toluene were used to obtain 22.1 g (72%) of P1-1 using the final product Synthesis Example 1.

(2) P1 Synthesis of -7

<Reaction Scheme 23>

Sub 2-6 (15g, 42.9mmol), Sub 1-4 (28.4g, 47.2mmol), Pd 2 (dba) 3 (1.97g, 2.15mmol), P (t-Bu) 3 (0.87g, 4.3mmol ), NaO t- Bu (12.4 g, 128.8 mmol) and 450 mL of toluene were used to obtain 26.1 g (70%) of P1-7 using the final product Synthesis Example 1.

(3) P1 Synthesis of -17

<Reaction Scheme 24>

Sub 2-44 (15g, 28.9mmol), Sub 1-18 (11.8g, 31.8mmol), Pd 2 (dba) 3 (1.32g, 1.45mmol), P (t-Bu) 3 (0.59g, 2.89mmol ), NaO t- Bu (8.34 g, 86.8 mmol) and 304 mL of toluene were used to obtain 17.1 g (73%) of P1-17 using the final product Synthesis Example 1.

(4) P2 Synthesis of -5

<Reaction Scheme 25>

Sub 2-23 (15g, 61.1mmol), Sub 1-31 (30.2g, 67.3mmol), Pd 2 (dba) 3 (2.8g, 3.06mmol), P (t-Bu) 3 (1.24g, 6.11mmol ), NaO t- Bu (17.63 g, 183.4 mmol) and 642 mL of toluene were used to obtain 28.5 g (76%) of P2-5 using the final product Synthesis Example 1.

(5) P2 Synthesis of -17

<Reaction Scheme 26>

Sub 2-48 (15g, 22.1mmol), Sub 1-36 (6.88g, 24.3mmol), Pd 2 (dba) 3 (1.01g, 1.10mmol), P (t-Bu) 3 (0.45g, 2.21mmol ), NaO t- Bu (6.37 g, 66.3 mmol) and 232 mL of toluene were used to obtain 13.8 g (71%) of P2-17 using Synthesis Example 1 of the final product.

(6) P3 Synthesis of -6

<Reaction Scheme 27>

Sub 2-4 (15g, 57.85mmol), Sub 1-42 (32.2g, 63.63mmol), Pd 2 (dba) 3 (2.64g, 2.89mmol), P (t-Bu) 3 (1.17g, 5.78mmol ), NaO t- Bu (16.7 g, 173.5 mmol) and 607 mL of toluene were used to obtain 30 g (76%) of P3-6 using the final product Synthesis Example 1.

(7) P3 Synthesis of -10

<Reaction Scheme 28>

Sub 2-8 (15g, 36.5mmol), Sub 1-40 (15.65g, 40.2mmol), Pd 2 (dba) 3 (1.67g, 1.83mmol), P (t-Bu) 3 (0.74g, 3.65mmol ), NaO t- Bu (10.5 g, 109.6 mmol) and 383 mL of toluene were used to obtain 20.2 g (77%) of P3-10 using the final product Synthesis Example 1.

(8) P3 Synthesis of -25

<Reaction Scheme 29>

Sub 2-23 (34.6g, 141mmol), Sub 1-48 (30g, 64.08mmol), Pd 2 (dba) 3 (5.86g, 6.41mmol), P (t-Bu) 3 (2.6g, 12.8mmol) , NaO t- Bu (40.6 g, 423 mmol) and toluene (845 mL) were used to obtain 37.8 g (74%) of P3-25 using the final product Synthesis Example 2.

(9) P4 Synthesis of -9

<Reaction Scheme 30>

Sub 2-21 (15g, 46.1mmol), Sub 1-54 (30.3g, 50.7mmol), Pd 2 (dba) 3 (2.11g, 2.3mmol), P (t-Bu) 3 (0.93g, 4.6mmol ), NaO t- Bu (13.3 g, 138.3 mmol) and 484 mL of toluene were used to obtain 26.4 g (68%) of P4-9 using the final product Synthesis Example 1.

(10) P4 Synthesis of -23

<Reaction Scheme 31>

Sub 2-27 (15g, 46.7mmol), Sub 1-59 (26.9g, 51.3mmol), Pd 2 (dba) 3 (2.14g, 2.33mmol), P (t-Bu) 3 (0.94g, 4.67mmol ), NaO t- Bu (13.5 g, 140 mmol) and 490 mL of toluene were used to obtain 26.7 g (75%) of P4-23 using the final product Synthesis Example 1.

(11) P4 Synthesis of -29

<Reaction equation 32>

Sub 2-36 (15g, 39.7mmol), Sub 1-57 (22.9g, 43.7mmol), Pd 2 (dba) 3 (1.82g, 1.99mmol), P (t-Bu) 3 (0.80g, 3.97mmol ), NaO t- Bu (11.5 g, 119.2 mmol) and 417 mL of toluene were used to obtain 23.1 g (71%) of P4-29 using the final product Synthesis Example 1.

On the other hand, FD-MS of the compounds P1-1 to P1-40, P2-1 to P2-30, P3-1 to P3-30 and P4-1 to P4-30 of the present invention prepared according to the above synthesis example The values are shown in Table 4 below.

[Table 4]

Evaluation of manufacturing of organic electric device

[ Example  1]: Green organic electroluminescent device ( Hole transport layer )

An organic electroluminescent device was prepared according to a conventional method using a compound according to an embodiment of the present invention as a hole transport layer material. First, N ¹ on the ITO layer (anode) formed on an organic substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 -phenylbenzene-1,4-diamine (abbreviated as "2-TNATA" hereinafter) was vacuum-deposited to a thickness of 60 nm to form a hole injection layer. Subsequently, the compound P1-1 of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Then, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ ") was used as a host material on the hole transport layer, and 4,4'-N, N'-dicarbazole- Quot; as a dopant material) was doped in a weight ratio of 90:10, and vacuum evaporated to a thickness of 30 nm to form a light emitting layer. Next, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum- (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer. Thereafter, an electron injection layer was formed by depositing LiF, which is an alkali metal halide, to a thickness of 0.2 nm on the electron transport layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  2] to [ Example  61] green organic electroluminescent device ( Hole transport layer )

An organic electroluminescent device was prepared in the same manner as in Example 1 except that one of the compounds of the present invention shown in Table 5 below was used instead of the compound P1-1 of the present invention as a hole transport layer material.

[ Comparative Example  1] to [ Comparative Example  5]

Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 3, Comparative Example 4, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were used instead of the compound P1-1 of the present invention as the hole transport layer material In Example 5, an organic electroluminescence device was prepared in the same manner as in Example 1 except that Comparative Compound 5 was used.

&Lt; Comparative Compound 1 > < Comparative Compound 2 > < Comparative Compound 3 &

,

,

,

,

&Lt; Comparative Compound 4 > < Comparative Compound 5 >

,

,

A forward bias DC voltage was applied to the organic electroluminescent devices prepared in Examples 1 to 61 and Comparative Examples 1 to 5 of the present invention, and electroluminescence (EL) characteristics were measured with a photoresearch PR-650 And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 5 below.

[Table 5]

As can be seen from the results of Table 5, it can be confirmed that the organic electroluminescence device using the compound of the present invention as a material of the hole transport layer exhibits high efficiency and long lifetime.

In detail, it was confirmed that the efficiency and lifetime of NPB, which is generally widely used as a hole transporting layer, are increased more than that of NPB, and that the number of carbon atoms in the ring containing X ¹ is smaller than that of the compound of the present invention by one It was confirmed that the device using the compound of the present invention exhibited a higher efficiency and a longer lifetime than the comparative compounds 2 to 5 (pentagonal rings).

This is the compound of the present invention the ring is six imprinted containing X ^1, increases the ring packing density (packing density) than 5 engraved Comparative Compound 2 to Comparative Compound 5 that includes X ^1, while the transport of holes easily, hole As a result, it is considered that the efficiency is increased by improving the charge balance in the light emitting layer. Further, since the packing density is increased in the case of the lifetime, the relatively low driving voltage and the Joule heat And the thermal stability is increased and the lifetime is increased.

In the case where X ¹ does not form a ring (P2-17, P2-18 and P3-17), the HOMO value is lowered due to the terminal naphthyl group. As a result, holes are trapped and the charge balance in the light emitting layer is improved, Respectively.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 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

Claims (10)

A compound represented by the following formula (1):
&Lt; Formula 1 >

In Formula 1,
Ar ^a is represented by the following general formula (2), Ar ^b is represented by the following general formula (3), Ar ^c is a C ₆ -C ₂₄ aryl group; A fluorenyl group; And a C ₂ -C ₂₄ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P;
&Lt; Formula 2 >< EMI ID =

In the above Formulas 2 and 3,
m and n are each independently an integer of 0 or 1,
X ¹ is N (R '), O, or is one of S, X ² is N (R'), O, S or C (R ') (R " ) and one wherein R in the X ^1' is , A C ₆ -C ₂₄ aryl group, a fluorenyl group, a C ₄ -C ₁₂ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N and S, and a C ₁ -C ₂₀ alkyl group ; Wherein R 'and R "of X ² are independently of each other a C ₆ -C ₂₄ aryl group; A fluorenyl group; And a C ₁ -C ₂₀ alkyl group,
L ₁ is a single bond; A C ₆ -C ₁₂ arylene group; A fluorenylene group; And O, N, S, a divalent C ₂ -C ₁₂ containing at least one heteroatom selected from the group consisting of Si and P heterocyclic group; is selected from the group consisting of,
L ₂ is a single bond; Or a C ₆ -C ₁₂ arylene group,
l is an integer of 0 to 4, o is an integer of 0 to 3, p is an integer of 3, q is an integer of 6,
R ¹ and R ² are, independently of each other, i) deuterium; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; And -L ₃ -N (R ⁵ ) (R ⁶ ); or ii) adjacent groups may be bonded to each other to form at least one ring, wherein R ¹ And R &lt; ² &gt; are defined as defined in i) above,
R ³ and R ⁴ are hydrogen;
L &lt; ₃ &gt; is a single bond; Or a C ₆ -C ₁₂ arylene group,
R ⁵ and R ⁶ are, independently of each other, a C ₆ -C ₂₄ aryl group; , And; or O, N and S, at least one hetero atom heterocyclic group of C ₅ -C ₂₀ comprising selected from the group consisting of
The R ⁵ and R ⁶ , L ₃ (excluding a single bond), R ⁵ or L ₃ (excluding a single bond) and R ⁶ may combine with each other to form a heterocyclic compound containing N, ,
The aryl group, the fluorenyl group, the heterocyclic group, the alkyl group, the alkenyl group, the alkynyl group, the arylene group and the fluorenylene group are each independently selected from the group consisting of deuterium; halogen; Cyano; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ An aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N and S; And ^{_{-L 3 -N (R 5) (}} R 6); may be optionally substituted with one or more substituents selected from the group consisting of. The method according to claim 1,
The compound of formula (2) is represented by one of the following formulas:
&Lt; Formula 4 >< EMI ID =

In the above formulas 4 to 6, L ₁ , R ', R ³ , R ⁴ , p and q are the same as defined in claim 1. The method according to claim 1,
The compound of formula (3) is represented by one of the following formulas:
&Lt; Formula 8 >< EMI ID =

In the general formulas (8) to (11), R ', R ", R ¹ , R ² , L ₂ , l and o are the same as defined in claim 1. The method according to claim 1,
Wherein at least one of R &lt; ¹ &gt; and R &lt; ² &gt; comprises deuterium. The method according to claim 1,
A compound characterized by being one of the following compounds:

. A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode,
Wherein the organic material layer contains the compound of any one of claims 1 to 5. The method according to claim 6,
The compound is contained in at least one layer of the hole injection layer, the hole transport layer, the luminescent auxiliary layer and the luminescent layer of the organic material layer,
Wherein the compound is a homologous compound or two or more different kinds of compounds. The method according to claim 6,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a film coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device of claim 6; And
And a control unit for driving the display device. 10. The method of claim 9,
Wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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