KR102502430B1 - 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 compound capable of improving luminous efficiency, stability and lifespan of a device, an organic electric device using the same, and an electronic device thereof.

Description

Compound for organic electric element, organic electric element using the same and electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, 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 may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

In the case of bis-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, band gaps (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. are different depending on the number of rings, fused position, and type and arrangement of heteroatoms. this has been going on

In a phosphorescent organic electronic device using a phosphorescent dopant material, the LUMO and HOMO levels of the host material are factors that greatly affect the efficiency and lifespan of the organic electronic device. Accordingly, reduction in efficiency and reduction in lifetime due to control of charge balance in the light emitting layer, quenching of dopants, and light emission at the interface of the hole transport layer can be prevented.

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 Activated Delayed Fluorescent), Exciplex, etc., and in particular, identifying the energy transfer method from the host material to the dopant material. A lot of research is going on.

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

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

As such, there are various factors that affect efficiency and lifetime depending on the way energy is transferred from the host material to the dopant material, and since the energy transfer method is different depending on the material, stable and efficient host materials for organic electric devices have yet to be developed. This is not done enough. Therefore, development of new materials is continuously required, and in particular, development of a host material for the light emitting layer is urgently required.

KR 10-1170666 B1

The present invention has been proposed to solve the above problems of the phosphorescent host material, and it is possible to control the charge balance in the light emitting layer through the control of the HOMO level of the host material of the phosphorescent light emitting organic electric device including the phosphorescent dopant, and to improve the efficiency and lifetime. An object of the present invention is to provide an improved compound, an organic electric device using the same, and an electronic device thereof.

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

The present invention is an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is represented by the following formula (1) It provides an organic electric device characterized in that it comprises a first host compound and a second host compound represented by the following formula (2).

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

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

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

Hereinafter, it will be described in detail with reference to embodiments of the present invention. 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.

Also, terms such as first, second, A, B, (a), and (b) may be used in describing the components of the present invention. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element is or may be directly connected to the other element, but there is another element between the elements. It will be understood that elements may be “connected”, “coupled” or “connected”.

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

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

As used herein, unless otherwise specified, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, and includes a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and the like. A radical of a saturated aliphatic functional group, including an alkyl group, a cycloalkyl-substituted alkyl group.

As used herein, the term "haloalkyl group" or "halogenalkyl group" refers to an alkyl group substituted with a halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that one or more of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

As used herein, the term "alkenyl group", "alkenyl group" or "alkynyl group" has a double bond or triple bond of 2 to 60 carbon atoms, respectively, and includes a straight or branched chain group, unless otherwise specified. , but is not limited thereto.

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

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms, unless otherwise specified, and is limited thereto. It is not.

As used herein, 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, 2 to 60 It has a carbon number of, but is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" 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 herein have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group refers to a single-ring or multi-ring aromatic ring, and includes an aromatic ring formed by bonding or reacting with adjacent substituents. For example, the aryl group may be a phenyl group, a biphenyl group, a 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 carbon atoms described herein.

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

The term "heteroalkyl" as used herein, unless otherwise specified, means an alkyl containing one or more heteroatoms. As used herein, the term "heteroaryl group" or "heteroarylene group" refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is limited thereto It does not, and includes at least one of a single ring and a multi-ring, and may be formed by combining adjacent functional groups.

As used herein, the term "heterocyclic group" includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group, unless otherwise specified. Contains an aromatic ring. It may also be formed by combining adjacent functional groups.

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

In addition, the "heterocyclic group" may 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" as used herein means an aliphatic hydrocarbon ring having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other hetero compounds or heteroradicals other than the aforementioned hetero compounds include, but are not limited to, one or more heteroatoms.

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

Unless otherwise specified, the term "ether" as used herein is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a carbon atom of 6 to 30 carbon atoms. It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

In addition, unless explicitly stated otherwise, “substituted” in the term “substituted or unsubstituted” as used herein means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, deuterium-substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ ~ C ₂₀ means substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponential definition of the following chemical formula.

Here, when a is an integer of 0, substituent R ¹ means that it does not exist, that is, when a is 0, it means that hydrogen is bonded to all carbons forming the benzene ring. It may be omitted and the chemical formula or compound may be described. When a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3, each bond is as follows, wherein R ¹ may be the same or different from each other. And, when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omitted.

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

The present invention is an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer having the formula An organic electric device comprising a first host compound represented by 1 and a second host compound represented by Chemical Formula 2 is provided.

{In Formula 1, Formula 1-1 and Formula 2,

M is a C ₆ -C ₆₀ arylene group or Formula 1-1;

X ¹ is S or O;

X ² is NL ⁵ -Ar ⁶ , O, S or CR ^a R ^b ;

X ³ is NL ⁸ -Ar ⁸ , O, S or CR ^c R ^d ;

A, B, C, D, E, F, G and H are each independently a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heterocyclic group,

C is bonded to L ³ , D is bonded to L ⁴ ,

R ^a , R ^b , R ^c and R ^d are each independently hydrogen, deuterium; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group and C ₆ -C ₃₀ aryloxy group; selected from the group consisting of, R ^a and R ^b may bond to each other to form a spiro (spiro) compound,

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ may each independently represent a C ₆ -C ₆₀ aryl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy group; selected from the group consisting of, and Ar ¹ to Ar ⁸ may be bonded to each other to form a ring;

L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ may each independently be a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And C ₃ -C ₆₀ It is selected from the group consisting of an aliphatic hydrocarbon group,

Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group are each 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 alkynyl group; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; A C ₇ -C ₂₀ arylalkyl group and a 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 combine with each other to form a ring, where ' The term 'ring' refers to a C ₃ -C ₆₀ aliphatic ring, C ₆ -C ₆₀ aromatic ring, C ₂ -C ₆₀ hetero ring, or a fused ring composed of a combination thereof, and includes a saturated or unsaturated ring.}

Specifically, the present invention includes compounds in which A, B, C, D, E, and F are each independently represented by any one selected from the group consisting of Formulas a-1 to Formulas a-7 below.

{In the formula a-1 to formula a-7,

Z ¹ to Z ⁴⁸ are CR ^e or N;

However, Z ¹ to Z ⁴⁸ bonded to L ¹ to L ⁶ are carbon (C),

R ^e is the same as the definition of R ^a above,

* indicates the condensed position.}

In addition, the present invention provides a compound wherein L ¹ to L ⁶ are any one of the following formulas b-1 to b-13.

Formula b-11 Formula b-12 Formula b-13

{In the formula b-1 to formula b-13,

Y is NL ⁹ -Ar ⁹ , O, S or CR ^f R ^g ;

L ⁹ is the same as the definition of L ⁵ above,

Ar ⁹ is the same as the definition of Ar ⁶ above,

R ^f and R ^g are the same as the definition of R ^a above,

a, c, d, e are each independently an integer from 0 to 4, b is an integer from 0 to 6, f and g are independently an integer from 0 to 3, h is an integer from 0 to 2, i is an integer of 0 or 1;

R ¹ to R ³ are each independently hydrogen; heavy hydrogen; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^a -N (R ^h ) (R ⁱ ); is selected from the group consisting of, or when a, b, c, d, e, f and g are 2 or more, and when h is 2, respectively Multiple R ^{1 , multiple R 2} , multiple R ³ , or adjacent R ¹ and R ² , or R ^{2 and} R ³ , which are the same or different from each other, combine with each other to form an aromatic ring or a heteroaromatic ring can do,

wherein L ^a is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; and a C ₃ -C ₆₀ aliphatic hydrocarbon group; wherein R ^h and R ⁱ are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; It is selected from the group consisting of; a fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring;

Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ are independently CR ^j or N, and at least one of Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ is N,

R ^j is hydrogen; heavy hydrogen; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group; selected from the group consisting of, and adjacent R ¹ and R ^h may combine with each other to form an aromatic ring or a heteroaromatic ring.}

As another example, the present invention provides an organic electric device including a compound represented by the following Chemical Formula 1-2 in which at least one of Ar ¹ to Ar ⁵ in Chemical Formula 1 is provided.

{In Formula 1-2,

I and J are the same as the definition of A above,

X ⁴ is NL ¹¹ -Ar ¹⁰ , O, S or CR ^k R ^l ;

L ¹⁰ and L ¹¹ are the same as the definition of L ⁵ above,

Ar ¹⁰ is the same as the definition of Ar ⁶ above,

R ^k and R ^l are the same as the definition of R ^a above.}

In the present invention, the first host compound represented by Chemical Formula 1 includes a compound represented by Chemical Formula 3 below.

{In Formula 3,

X ¹ , X ² , Ar ¹ to Ar ⁵ , and Z ¹ to Z ⁴ are as defined above.}

Preferably, in the present invention, a compound in which X ¹ and X ² of Formula 1 are independently O or S is included.

In addition, the present invention includes a compound represented by any one of the following Chemical Formulas 4 to 7 as the second host compound represented by Chemical Formula 2.

{In Formula 4 to Formula 7,

E, F, G, H, L ⁶ , L ⁷ , L ⁸ , Ar ⁷ , Ar ⁸ , R ^c , R ^d are as defined above.}

More specifically, in the present invention, the first host compound represented by Chemical Formula 1 includes the following compounds 1-1 to 1-265.

In the present invention, the second host compound represented by Chemical Formula 2 includes the following compounds 2-1 to 2-135.

Referring to FIG. 1, the organic electric element 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. An organic material layer containing the compound represented by Chemical Formula 1 is provided between (180). In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

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

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

On the other hand, even in the same core, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents bonded thereto are also very important. It is important, especially when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is 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 a physical vapor deposition (PVD) method. For example, an anode is formed by depositing a metal or a metal oxide having conductivity 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 After forming an organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition, an auxiliary light emitting layer 151 may be further 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 includes one or more hole transport band layers between the first electrode and the light emitting layer, wherein the hole transport band layer includes a hole transport layer, a light emitting auxiliary layer, or both, and the hole transport band layer An organic electric device including the compound represented by Formula 1 is provided.

In addition, the present invention provides an organic electric element included in the light emitting layer by mixing the compounds represented by Formula 1 and Formula 2 at a ratio of 1:9 to 9:1, preferably 1:9 to 5 :5, more preferably 2:8 or 3:7, and included in the light emitting layer.

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

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

An organic electric device according to an embodiment of the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are arranged in parallel on a mutually flat surface, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is, and there is a color conversion material (CCM) method using electroluminescence by a blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using light from the electroluminescent layer. may also be applied to these WOLEDs.

In addition, the present invention is a display device including the organic electric element; and a controller for driving the display device.

In another aspect, the present invention provides an electronic device characterized in that the organic electric device is at least one of an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for monochromatic or white lighting. At this time, the electronic device may be a current or future wired/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 control, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, synthetic examples of the compounds represented by Chemical Formulas 1 and 2 and manufacturing examples of the organic electric device of the present invention will be described in detail with examples, but the present invention is not limited to the following examples. .

[ synthesis example One]

The compound represented by Formula 1 according to the present invention (final product 1) is disclosed in Korea Patent Registration No. 10-1614739 (registration notice dated 2016.04.18) and Korean Patent Application 2016-0110817 (filed on 2016.08.30) of the present applicant. It was prepared by the disclosed synthetic method. X ¹ , A, B, L ¹ to L ⁴ , M, Ar ¹ to Ar ⁵ are the same as those defined in Chemical Formula 1 above.

<Scheme 1>

[ synthesis example 2]

The compound represented by Chemical Formula 2 according to the present invention (final product 2) is synthesized by reacting Sub 3 and Sub 4 as in Scheme 2 below, but is not limited thereto. X ³ , E, F, G, H, L ⁶ , L ⁷ , and Ar ⁷ are the same as defined in Chemical Formula 2, and Hal ² is Br or Cl.

<Scheme 2>

I. Synthesis of Sub 3

Sub 3 of Reaction Scheme 2 is synthesized by the reaction pathway of Reaction Scheme 3 below, but is not limited thereto.

<Scheme 3>

The carbazole derivative used in the synthesis of Sub 3 is the applicant's Korean Registered Patent No. 10-1535606 (registration announcement on July 3, 2015), Korean Patent Application 2012-0152002 (filed on December 24, 2012), Korean application It was prepared by the synthesis method disclosed in Patent No. 2016-0025426 (filed on March 3, 2016).

A dibenzothiophene derivative or dibenzofuran, which is a starting material used in the synthesis of Sub 3, was prepared by the synthetic method disclosed in Korean Patent Application No. 2014-0074261 (filed on June 18, 2014) of the present applicant.

The fluorene derivative, which is a starting material used in the synthesis of Sub 3, is prepared by the synthesis method disclosed in Korean Patent Application No. 2013-0056221 (filed on May 20, 2013) and Korean Patent Application No. 2015-0083505 (filed on June 12, 2015) of the present applicant. It became.

1. Sub 3-1 synthesis example

After dissolving the starting material, 3-bromo-9 H -carbazole (47.03 g, 191.09 mmol) in THF (850 ml) in a round bottom flask, 9-phenyl-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl) -9H- carbazole (70.57 g, 191.09 mmol), Pd(PPh ₃ ) ₄ (6.62 g, 5.73 mmol), K ₂ CO ₃ (79.23 g, 573.28 mmol), Water (425 ml) was added and stirred at 80°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 64.79 g (yield: 83%) of the product.

2. Sub 3-19 synthesis example

9-([1,1'-biphenyl]-4-yl)-3- ( 4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl) -9H- carbazole (29.15 g, 65.46 mmol), Pd(PPh ₃ ) ₄ (2.27 g, 1.96 mmol), K ₂ CO ₃ (27.14 g, 196.38 mmol), THF (290 ml) and water (145 ml) were added and 24.43 g (yield: 77%) of the product was obtained using the Sub 3-1 synthesis method.

3. Sub 3-44 synthesis example

9-(4-(2,6-diphenylpyridin-4-yl)phenyl)-2- ( 4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) -9H- carbazole (40.30 g, 67.33 mmol), Pd(PPh ₃ ) ₄ (2.33 g, 2.02 mmol), K ₂ CO ₃ (27.91 g, 201.98 mmol) ), THF (300 ml), and water (150 ml) were added, and 26.62 g (yield: 62%) of a product was obtained using the Sub 3-1 synthesis method.

4. Sub 3-46 synthesis example

9-(naphthalen-2-yl)-1-(4,4,5,5 - tetramethyl-1,3,2-dioxaborolan- 2-yl) -9H -carbazole (29.32 g, 69.93 mmol), Pd(PPh ₃ ) ₄ (2.42 g, 2.10 mmol), K ₂ CO ₃ (28.99 g, 209.78 mmol), THF (300 ml), water (150 ml) was added and 18.60 g of product (yield: 58%) was obtained using the Sub 3-1 synthesis method.

5. Sub 3-57 synthesis example

9-([1,1'- biphenyl ]-3-yl)-1-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl) -9H- carbazole (37.15 g, 83.42 mmol), Pd(PPh ₃ ) ₄ (2.89 g, 2.50 mmol), K ₂ CO ₃ (34.59 g, 250.25 mmol), THF (370 ml) and water (185 ml) were added and 21.83 g (yield: 54%) of a product was obtained using the Sub 3-1 synthesis method.

6. Sub 3-62 synthesis example

9-([1,1'-biphenyl]-4-yl)-2- ( 4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl) -9H -carbazole (24.94 g, 55.99 mmol), Pd(PPh ₃ ) ₄ (1.94 g, 1.68 mmol), K ₂ CO ₃ (23.21 g, 167.97 mmol), THF (250 ml) and water (125 ml) were added and 23.06 g (yield: 85%) of a product was obtained using the Sub 3-1 synthesis method.

7. Sub 3-74 synthesis example

9-([1,1'-biphenyl]-3-yl)-3-(4,4,5,5-tetramethyl-1 to the starting material 2-bromo- 9H- carbazole (19.10 g, 77.61 mmol) ,3,2-dioxaborolan-2-yl) -9H- carbazole (34.56 g, 77.61 mmol), Pd(PPh ₃ ) ₄ (2.69 g, 2.33 mmol), K ₂ CO ₃ (32.18 g, 232.82 mmol), THF (340 ml) and water (170 ml) were added and 33.10 g (yield: 88%) of a product was obtained using the Sub 3-1 synthesis method.

8. Sub 3-92 synthesis example

5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[4,5] to the starting material 4-bromo- 9H -carbazole (15.12 g, 61.44 mmol) thieno[2,3-c]pyridine (19.12 g, 61.44 mmol), Pd(PPh ₃ ) ₄ (2.13 g, 1.84 mmol), K ₂ CO ₃ (25.47 g, 184.31 mmol), THF (270 ml), water (140 ml) was added and 14.86 g of product (yield: 69%) was obtained using the Sub 3-1 synthesis method.

9. Sub 3-96 synthesis example

2-(9,9-diphenyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1 to the starting material 1 - bromo- 9H- carbazole (16.61 g, 67.49 mmol), 3,2-dioxaborolane (29.99 g, 67.49 mmol), Pd(PPh ₃ ) ₄ (2.34 g, 2.02 mmol), K ₂ CO ₃ (27.98 g, 202.47 mmol), THF (300 ml), water (150 ml) was added and 24.81 g of product (yield: 76%) was obtained using the Sub 3-1 synthesis method.

10. Sub 3-112 synthesis example

2-(dibenzo[b,d]thiophen-3-yl)-4,4,5,5-tetramethyl-1,3,2 to the starting material 3-bromo- 9H -carbazole (18.40 g, 74.76 mmol) -dioxaborolane (23.19 g, 74.76 mmol), Pd(PPh ₃ ) ₄ (2.59 g, 2.24 mmol), K ₂ CO ₃ (31.00 g, 224.29 mmol), THF (320 ml) and water (160 ml) were added. 21.42 g (yield: 82%) of the product was obtained using the Sub 3-1 synthesis method.

11. Sub 3-113 synthesis example

2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2 to the starting material 3-bromo- 9H -carbazole (17.19 g, 69.85 mmol) -dioxaborolane (20.55 g, 69.85 mmol), Pd(PPh ₃ ) ₄ (2.42 g, 2.10 mmol), K ₂ CO ₃ (28.96 g, 209.54 mmol), THF (300 ml) and water (150 ml) were added. 18.63 g (yield: 80%) of the product was obtained using the Sub 3-1 synthesis method.

Compounds belonging to Sub 3 may be the following compounds, but are not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 3.

compound FD-MS compound FD-MS Sub 3-1 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-2 m/z=427.15 (C ₂₉ H ₁₈ FN ₃ =427.48) Sub 3-3 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-4 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-5 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-6 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-7 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-8 m/z=524.23 (C ₃₉ H ₂₈ N ₂ =524.67) Sub 3-9 m/z=514.15 (C ₃₆ H ₂₂ N ₂ S=514.65) Sub 3-10 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-11 m/z=485.19 (C ₃₅ H ₂₃ N ₃ =485.59) Sub 3-12 m/z = 561.22 (C ₄₁ H ₂₇ N ₃ =561.69) Sub 3-13 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-14 m/z = 513.23 (C ₃₈ H ₁₉ D ₅ N ₂ =513.65) Sub 3-15 m/z=598.20 (C ₄₄ H ₂₆ N ₂ O=598.71) Sub 3-16 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-17 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-18 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-19 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-20 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) Sub 3-21 m/z = 561.22 (C ₄₁ H ₂₇ N ₃ =561.69) Sub 3-22 m/z=558.21 (C ₄₂ H ₂₆ N ₂ =558.68) Sub 3-23 m/z = 690.34 (C ₄₉ H ₄₆ N ₂ Si = 691.01) Sub 3-24 m/z=644.20 (C ₄₄ H ₂₈ N ₄ S=644.80) Sub 3-25 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-26 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-27 m/z=558.21 (C ₄₂ H ₂₆ N ₂ =558.68) Sub 3-28 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-29 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-30 m/z=509.19 (C ₃₇ H ₂₃ N ₃ =509.61) Sub 3-31 m/z 514.15 (C ₃₆ H ₂₂ N ₂ S=514.65) Sub 3-32 m/z=584.23 (C ₄₄ H ₂₈ N ₂ =584.72) Sub 3-33 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) Sub 3-34 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) Sub 3-35 m/z=646.24 (C ₄₉ H ₃₀ N ₂ =646.79) Sub 3-36 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-37 m/z = 561.22 (C ₄₁ H ₂₇ N ₃ =561.69) Sub 3-38 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-39 m/z=558.21 (C ₄₂ H ₂₆ N ₂ =558.68) Sub 3-40 m/z=560.23 (C ₄₂ H ₂₈ N ₂ =560.70) Sub 3-41 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-42 m/z = 413.19 (C ₃₀ H ₁₅ D ₅ N ₂ =413.53) Sub 3-43 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-44 m/z=637.25 (C ₄₇ H ₃₁ N ₃ =637.79) Sub 3-45 m/z=586.22 (C ₄₂ H ₂₆ N ₄ =586.70) Sub 3-46 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-47 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-48 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-49 m/z=650.24 (C ₄₈ H ₃₀ N ₂ O=650.78) Sub 3-50 m/z=610.24 (C ₄₆ H ₃₀ N ₂ =610.76) Sub 3-51 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-52 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-53 m/z = 635.24 (C ₄₇ H ₂₉ N ₃ =635.77) Sub 3-54 m/z=537.20 (C ₃₇ H ₂₃ N ₅ =537.63) Sub 3-55 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-56 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-57 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-58 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) Sub 3-59 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-60 m/z=638.25 (C ₄₆ H ₃₀ N ₄ =638.77) Sub 3-61 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-62 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-63 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) Sub 3-64 m/z=560.23 (C ₄₂ H ₂₈ N ₂ =560.70) Sub 3-65 m/z=818.25 (C ₅₈ H ₃₄ N ₄ S=819.00) Sub 3-66 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-67 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-68 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-69 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-70 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) Sub 3-71 m/z=548.19 (C ₄₀ H ₂₄ N ₂ O=548.65) Sub 3-72 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.86) Sub 3-73 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.50) Sub 3-74 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60 Sub 3-75 m/z=459.17 (C ₃₃ H ₂₁ N ₃ =459.55) Sub 3-76 m/z=610.24 (C ₄₆ H ₃₀ N ₂ =610.76) Sub 3-77 m/z=638.25 (C ₄₆ H ₃₀ N ₄ =638.77) Sub 3-78 m/z=459.17 (C ₃₃ H ₂₁ N ₃ =459.55) Sub 3-79 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) Sub 3-80 m/z=662.25 (C ₄₈ H ₃₀ N ₄ =662.80) Sub 3-81 m/z = 658.24 (C ₅₀ H ₃₀ N ₂ =658.80) Sub 3-82 m/z=700.29 (C ₅₃ H ₃₆ N ₂ =700.89) Sub 3-83 m/z=349.09 (C ₂₄ H ₁₅ NS=349.45) Sub 3-84 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-85 m/z=409.15 (C ₃₀ H ₁₉ NO=409.49) Sub 3-86 m/z = 607.23 (C ₄₇ H ₂₉ N = 607.76) Sub 3-87 m/z=349.09 (C ₂₄ H ₁₅ NS=349.45) Sub 3-88 m/z=483.20 (C ₃₇ H ₂₅ N=483.61) Sub 3-89 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-90 m/z=580.17 (C ₃₉ H ₂₄ N ₄ S=580.71) Sub 3-91 m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 3-92 m/z=350.09 (C ₂₃ H ₁₄ N ₂ S=350.44) Sub 3-93 m/z=433.15 (C ₃₂ H ₁₉ NO=433.51) Sub 3-94 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) Sub 3-95 m/z=541.19 (C ₃₉ H ₂₇ NS=541.71) Sub 3-96 m/z=483.20 (C ₃₇ H ₂₅ N=483.61) Sub 3-97 m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 3-98 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-99 m/z=503.15 (C ₃₄ H ₂₁ N ₃ S=503.62) Sub 3-100 m/z=435.14 (C ₃₀ H ₁₇ N ₃ O=435.49) Sub 3-101 m/z=481.18 (C ₃₇ H ₂₃ N=481.60) Sub 3-102 m/z=459.16 (C ₃₄ H ₂₁ NO=459.55) Sub 3-103 m/z=475.14 (C ₃₄ H ₂₁ NS=475.61) Sub 3-104 m/z=359.17 (C ₂₇ H ₂₁ N=359.47) Sub 3-105 m/z=428.11 (C ₂₇ H ₁₆ N ₄ S=428.51) Sub 3-106 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-107 m/z=349.09 (C ₂₄ H ₁₅ NS=349.45) Sub 3-108 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-109 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) Sub 3-110 m/z=359.17 (C ₂₇ H ₂₁ N=359.47) Sub 3-111 m/z=483.16 (C ₃₆ H ₂₁ NO=483.57) Sub 3-112 m/z=349.09 (C ₂₄ H ₁₅ NS=349.45) Sub 3-113 m/z = 333.12 (C ₂₄ H ₁₅ NO = 333.39) Sub 3-114 m/z=459.20 (C ₃₅ H ₂₅ N=459.59) Sub 3-115 m/z=656.20 (C ₄₅ H ₂₈ N ₄ S=656.81) Sub 3-116 m/z=533.21 (C ₄₁ H ₂₇ N=533.67)

II. Synthesis of Sub 4

Sub 4 of Reaction Scheme 2 is synthesized by the reaction pathway of Reaction Scheme 4 below, but is not limited thereto. At this time, Hal ¹ and Hal ² are Br or Cl.

<Scheme 4>

1. Sub 4-37 synthesis example

After dissolving the starting material, 4-bromo-2-chloro-6-phenylpyrimidine (CAS Registry Number: 1412955-57-7) (21.85 g, 81.07 mmol) in THF (280 ml) in a round bottom flask, 4,4, 5,5-tetramethyl-2-(naphthalen-2-yl)-1,3,2-dioxaborolane (CAS Registry Number: 256652-04-7) (22.66 g, 89.17 mmol), Pd(PPh ₃ ) ₄ (3.75 g, 3.24 mmol), K ₂ CO ₃ (33.61 g, 243.20 mmol), water (140 ml) and stirred at 90 °C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 19.52 g (yield: 76%) of the product.

2. Sub 4-46 synthesis example

2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl)pyrimidine (CAS Registry Number: 1402237-88-0) (29.73 g, 83.00 mmol), Pd(PPh ₃ ) ₄ (3.49 g, 3.02 mmol), K ₂ CO ₃ (31.28 g, 226.36 mmol), THF (260 ml) and water (130 ml) were added and 21.33 g (yield: 73%) of the product was obtained using the Sub 4-37 synthesis method.

3. Sub 4-68 synthesis example

(1) Synthesis of Sub 4-I-68

The starting material, 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was added to urea (CAS Registry Number: 57-13-6) (168.69 g, 401.25 mmol) in a round bottom flask. 2808.75 mmol) and stirred at 160 °C. After confirming the reaction by TLC, the mixture was cooled to 100° C., water (200 ml) was added, and the mixture was stirred for 1 hour. Upon completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water and dried to obtain 63.86 g of the product (yield: 75%).

(2) Synthesis of Sub 4-II-68

Sub 4-I-68 (63.86 g, 300.94 mmol) obtained in the above synthesis was dissolved in POCl ₃ (200 ml) at room temperature in a round bottom flask, and N , N -Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise thereto. Then, it was stirred at 90°C. Upon completion of the reaction, after concentrating, ice water (500 ml) was added and the mixture was stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g of product (yield: 90%).

(3) Synthesis of Sub 4-68

4,4,5,5-tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane (CAS Registry Number: 68716-52-9) (30.36 g, 119.45 mmol), Pd(PPh ₃ ) ₄ (5.02 g, 4.34 mmol), K ₂ CO ₃ (45.03 g, 325.79 mmol), THF (380 ml), water (190 ml) were added and the product was 22.21 g using the Sub 4-37 synthesis above (yield: 60 %) was obtained.

4. Sub 4-86 synthesis example

4,4,5,5-tetramethyl to the starting material 2,4-dichlorobenzo[4,5]thieno[3,2- d ]pyrimidine (CAS Registry Number: 160199-05-3) (38.00 g, 148.95 mmol) -2-phenyl-1,3,2-dioxaborolane (CAS Registry Number: 24388-23-6) (33.44 g, 163.84 mmol), Pd(PPh ₃ ) ₄ (6.88 g, 5.96 mmol), K ₂ CO ₃ ( 61.76 g, 446.85 mmol), THF (520 ml) and water (260 ml) were added and 17.68 g (yield: 40%) of the product was obtained using the Sub 4-37 synthesis method.

5. Subs 4-88 synthesis example

2-(dibenzo[b,d] starting material 2,4-dichlorobenzo[4,5]thieno[3,2- d ]pyrimidine (CAS Registry Number: 160199-05-3) (35.15 g, 137.78 mmol) furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 947770-80-1) (44.58 g, 151.56 mmol), Pd(PPh ₃ ) ₄ (6.37 g, 5.51 mmol), K ₂ CO ₃ (57.13 g, 413.33 mmol), THF (480 ml), water (240 ml) were added and the product was 22.92 g (yield: 43 %) was obtained.

6. Sub 4-92 synthesis example

4,4,5,5-tetramethyl-2-phenyl-1 to the starting material 2,4-dichlorobenzofuro[2,3-d]pyrimidine (CAS Registry Number: 1801325-92-7) (41.43 g, 173.30 mmol) ,3,2-dioxaborolane (CAS Registry Number: 24388-23-6) (38.90 g, 190.63 mmol), Pd(PPh ₃ ) ₄ (8.01 g, 6.93 mmol), K ₂ CO ₃ (71.86 g, 519.91 mmol) , THF (600 ml), and water (300 ml) were added to obtain 18.49 g of product (yield: 38%) using the Sub 4-37 synthesis method.

Compounds belonging to Sub 4 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 4.

compound FD-MS compound FD-MS Sub 4-1 m/z = 155.96 (C ₆ H ₅ Br = 157.01) Sub 4-2 m/z=312.09 (C ₁₅ H ₂₅ BrSi=313.35) Sub 4-3 m/z=173.95 (C ₆ H ₄ BrF=175.00) Sub 4-4 m/z = 160.99 (C ₆ D ₅ Br = 162.04) Sub 4-5 m/z = 205.97 (C ₁₀ H ₇ Br = 207.07) Sub 4-6 m/z = 205.97 (C ₁₀ H ₇ Br = 207.07) Sub 4-7 m/z = 231.99 (C ₁₂ H ₉ Br = 233.11) Sub 4-8 m/z=241.05 (C ₁₂ D ₉ Br=242.16) Sub 4-9 m/z = 231.99 (C ₁₂ H ₉ Br = 233.11) Sub 4-10 m/z=308.02 (C ₁₈ H ₁₃ Br=309.21) Sub 4-11 m/z=308.02 (C ₁₈ H ₁₃ Br=309.21) Sub 4-12 m/z=282.00 (C ₁₆ H ₁₁ Br=283.17) Sub 4-13 m/z=282.00 (C ₁₆ H ₁₁ Br=283.17) Sub 4-14 m/z=282.00 (C ₁₆ H ₁₁ Br=283.17) Sub 4-15 m/z=282.00 (C ₁₆ H ₁₁ Br=283.17) Sub 4-16 m/z=282.00 (C ₁₆ H ₁₁ Br=283.17) Sub 4-17 m/z = 255.99 (C ₁₄ H ₉ Br = 257.13) Sub 4-18 m/z = 255.99 (C ₁₄ H ₉ Br = 257.13) Sub 4-19 m/z=306.00 (C ₁₈ H ₁₁ Br=307.19) Sub 4-20 m/z = 279.99 (C ₁₆ H ₉ Br = 281.15) Sub 4-21 m/z = 245.97 (C ₁₂ H ₇ BrO = 247.09) Sub 4-22 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) Sub 4-23 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) Sub 4-24 m/z = 295.98 (C ₁₆ H ₉ BrO = 297.15) Sub 4-25 m/z = 322.00 (C ₁₈ H ₁₁ BrO = 323.19) Sub 4-26 m/z = 272.02 (C ₁₅ H ₁₃ Br = 273.17) Sub 4-27 m/z=396.05 (C ₂₅ H ₁₇ Br=397.32) Sub 4-28 m/z=394.04 (C ₂₅ H ₁₅ Br=395.30) Sub 4-29 m/z=322.04 (C ₁₉ H ₁₅ Br=322.04) Sub 4-30 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.21) Sub 4-31 m/z=319.00 (C ₁₈ H ₁₀ BrN=320.19) Sub 4-32 m/z=309.02 (C ₁₇ H ₁₂ BrN=310.19) Sub 4-33 m/z=309.02 (C ₁₇ H ₁₂ BrN=310.19) Sub 4-34 m/z=385.05 (C ₂₃ H ₁₆ BrN=386.29) Sub 4-35 m/z = 371.94 (C ₁₆ H ₉ BrN ₂ S ₂ =373.29) Sub 4-36 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-37 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.24) Sub 4-38 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.28) Sub 4-39 m/z=526.10 (C ₃₃ H ₂₃ BrN ₂ =527.47) Sub 4-40 m/z=416.00 (C ₂₂ H ₁₃ BrN ₂ S=417.32) Sub 4-41 m/z=387.04 (C ₂₁ H ₁₄ BrN ₃ =388.27) Sub 4-42 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-43 m/z=562.10 (C ₃₆ H ₂₃ BrN ₂ =563.50) Sub 4-44 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.24) Sub 4-45 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.28) Sub 4-46 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.28) Sub 4-47 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-48 m/z=240.02 (C ₁₂ H ₅ ClN ₄ =240.65) Sub 4-49 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 4-50 m/z=311.01 (C ₁₅ H ₁₀ BrN ₃ =312.17) Sub 4-51 m/z=361.02 (C ₁₉ H ₁₂ BrN ₃ =362.23) Sub 4-52 m/z=411.04 (C ₂₃ H ₁₄ BrN ₃ =412.29) Sub 4-53 m/z=411.04 (C ₂₃ H ₁₄ BrN ₃ =412.29) Sub 4-54 m/z=397.10 (C ₂₁ H ₄ D ₁₀ BrN ₃ =398.33) Sub 4-55 m/z=437.05 (C ₂₅ H ₁₆ BrN ₃ = 438.33) Sub 4-56 m/z=511.07 (C ₃₁ H ₁₈ BrN ₃ =512.41) Sub 4-57 m/z=416.99 (C ₂₁ H ₁₂ BrN ₃ S=418.31) Sub 4-58 m/z=451.03 (C ₂₅ H ₁₄ BrN ₃ O=452.31) Sub 4-59 m/z=507.00 (C ₂₇ H ₁₄ BrN ₃ OS=508.39) Sub 4-60 m/z=387.04 (C ₂₁ H ₁₄ BrN ₃ =388.27) Sub 4-61 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) Sub 4-62 m/z=297.11 (C ₁₈ H ₄ D ₇ ClN ₂ =297.79) Sub 4-63 m/z=291.06 (C ₁₇ H ₁₀ ClN ₃ =291.74) Sub 4-64 m/z=316.08 (C ₂₀ H ₁₃ ClN ₂ =316.79) Sub 4-65 m/z=346.03 (C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub 4-66 m/z=341.07 (C ₂₁ H ₁₂ ClN ₃ =341.80) Sub 4-67 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) Sub 4-68 m/z=340.08 (C ₂₂ H ₁₃ ClN ₂ =340.81) Sub 4-69 m/z=366.09 (C ₂₄ H ₁₅ ClN ₂ =366.85) Sub 4-70 m/z=396.05 (C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub 4-71 m/z=406.09 (C ₂₆ H ₁₅ ClN ₂ O=406.87) Sub 4-72 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.24) Sub 4-73 m/z=182.00 (C ₈ H ₄ ClFN ₂ =182.58) Sub 4-74 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) Sub 4-75 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) Sub 4-76 m/z=316.08 (C ₂₀ H ₁₃ ClN ₂ =316.79) Sub 4-77 m/z=346.03 (C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub 4-78 m/z=406.09 (C ₂₆ H ₁₅ ClN ₂ O=406.87) Sub 4-79 m/z=340.08 (C ₂₂ H ₁₃ ClN ₂ =340.81) Sub 4-80 m/z=366.09 (C ₂₄ H ₁₅ ClN ₂ =366.85) Sub 4-81 m/z=340.08 (C ₂₂ H ₁₃ ClN ₂ =340.81) Sub 4-82 m/z=390.09 (C ₂₆ H ₁₅ ClN ₂ =390.87) Sub 4-83 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.24) Sub 4-84 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.24) Sub 4-85 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) Sub 4-86 m/z=296.02 (C ₁₆ H ₉ ClN ₂ S=296.77) Sub 4-87 m/z=346.03 (C ₂₀ H ₁₁ ClN ₂ S=346.83) Sub 4-88 m/z=386.03 (C ₂₂ H ₁₁ ClN ₂ OS=386.85) Sub 4-89 m/z=386.03 (C ₂₂ H ₁₁ ClN ₂ OS=386.85) Sub 4-90 m/z=357.07 (C ₂₁ H ₁₂ ClN ₃ O=357.80) Sub 4-91 m/z=396.05 (C ₂₄ H ₁₃ ClN ₂ S=396.89) Sub 4-92 m/z=280.04 (C ₁₆ H ₉ ClN ₂ O=280.71) Sub 4-93 m/z=330.06 (C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub 4-94 m/z=396.10 (C ₂₅ H ₁₇ ClN ₂ O=396.87) Sub 4-95 m/z=356.11 (C ₂₃ H ₁₇ ClN ₂ =356.85) Sub 4-96 m/z=270.00 (C14H7ClN2S=270.73) Sub 4-97 m/z=456.10 (C ₃₀ H ₁₇ ClN ₂ O=456.93) Sub 4-98 m/z=421.03 (C ₂₂ H ₈ D ₅ BrN ₂ S=422.35) Sub 4-99 m/z=416.00 (C ₂₂ H ₁₃ BrN ₂ S=417.32) Sub4-100 m/z=350.04 (C ₁₉ H ₁₅ BrN ₂ =351.25) Sub4-101 m/z=386.03 (C ₂₂ H ₁₁ ClN ₂ OS=386.85) Sub4-102 m/z=296.02 (C ₁₆ H ₉ ClN ₂ S=296.77) Sub4-103 m/z=280.04 (C ₁₆ H ₉ ClN ₂ O=280.71) Sub4-104 m/z=280.04 (C ₁₆ H ₉ ClN ₂ O=280.71) Sub4-105 m/z=380.07 (C ₂₄ H ₁₃ ClN ₂ O=380.83) Sub4-106 m/z=219.99 (C ₁₀ H ₅ ClN ₂ S=220.67) Sub4-107 m/z=306.06 (C ₁₈ H ₁₁ ClN ₂ O=306.75) Sub4-108 m/z = 237.95 (C ₁₀ H ₇ BrS = 239.13) Sub4-109 m/z=297.02 (C ₁₆ H ₁₂ BrN=298.18) Sub4-110 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) Sub4-111 m/z=257.98 (C ₁₂ H ₇ BrN ₂ =259.11)

III. Synthesis of Final Product 2

After dissolving Sub 3 (1 equivalent) in toluene in a round bottom flask, Sub 4 (1.1 equivalent), Pd ₂ (dba) ₃ (0.03 equiv.), ( t -Bu) ₃ P (0.06 equiv.), NaO t -Bu (3 equiv.) were stirred at 100°C. After the reaction was completed, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain Final product 2.

1. 2-2 synthesis example

After dissolving Sub 3-1 (8.62 g, 21.10 mmol) obtained in the above synthesis with toluene (220 ml) in a round bottom flask, Sub 4-11 (CAS Registry Number: 1762-84-1) (7.18 g, 23.21 mmol) ), Pd ₂ (dba) ₃ (0.58 g, 0.63 mmol), P( t -Bu) ₃ (0.26 g, 1.27 mmol), NaO t -Bu (6.08 g, 63.30 mmol) were added and stirred at 100 °C. . After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 10.62 g (yield: 79%) of the product.

2. 2-3 synthesis example

Sub 4-30 (CAS Registry Number: 94994-62-4) (6.50 g, 20.17 mmol), Pd ₂ (dba) ₃ (0.50 g, 0.55 mmol) P( t -Bu) ₃ (0.22 g, 1.10 mmol), NaO t -Bu (5.29 g, 55.01 mmol), and toluene (195 ml) were added, and the product 10.01 g (yield) was obtained using the above 2-2 synthesis method : 84%) was obtained.

3. 2-4 synthesis example

Sub 4-50 (CAS Registry Number: 80984-79-8) (6.35 g, 20.33 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.55 mmol) P( t -Bu) ₃ (0.22 g, 1.11 mmol), NaO t -Bu (5.33 g, 55.45 mmol), and toluene (195 ml) were added to obtain 10.17 g of product (yield) using the above 2-2 synthesis method : 86%) was obtained.

4. 2-10 synthesis example

Sub 4-61 (CAS Registry Number: 29874-83-7) (5.25 g, 21.81 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol) P( t -Bu) ₃ (0.24 g, 1.19 mmol), NaO t -Bu (5.72 g, 59.49 mmol), and toluene (210 ml) were added to obtain a product of 9.84 g (yield) using the above 2-2 synthesis method : 81%) was obtained.

5. 2-14 synthesis example

Sub 4-74 (CAS Registry Number: 7065-92-1) (6.44 g, 26.74 mmol), Pd ₂ (dba) ₃ (0.67 g, 0.73 mmol) P( t -Bu) ₃ (0.30 g, 1.46 mmol), NaO t -Bu (7.01 g, 72.93 mmol), and toluene (255 ml) were added to obtain a product of 9.98 g (yield) using the above 2-2 synthesis method : 67%) was obtained.

6. 2-19 synthesis example

Sub 4-86 (5.15 g, 17.34 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.47 mmol) P( t -Bu) ₃ (0.19 g, 0.95 mmol), NaO t -Bu (4.55 g, 47.29 mmol), and toluene (165 ml) were added, and 8.96 g (yield: 85%) of a product was obtained using the above 2-2 synthesis method.

7. 2-31 synthesis example

Sub 4-74 (CAS Registry Number: 7065-92-1) (5.62 g, 23.33 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.64 mmol) P( t -Bu) ₃ (0.26 g, 1.27 mmol), NaO t -Bu (6.12 g, 63.64 mmol), and toluene (225 ml) were added to obtain a product of 9.35 g (yield) using the above 2-2 synthesis method : 64%) was obtained.

8. 2-54 synthesis example

Sub 4-36 (CAS Registry Number: 56181-49-8) (4.89 g, 15.73 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.43 mmol) P( t -Bu) ₃ (0.17 g, 0.86 mmol), NaO t -Bu (4.12 g, 42.90 mmol), and toluene (150 ml) were added and the product 8.69 g (yield) using the above 2-2 synthesis method : 70%) was obtained.

9. 2-60 synthesis example

Sub 4-92 (6.36 g, 22.67 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) P( t -Bu) ₃ (0.25 g, 1.24 mmol), NaO t -Bu (5.94 g, 61.82 mmol), and toluene (215 ml) were added, and 9.12 g (yield: 63%) of the product was obtained using the above 2-2 synthesis method.

10. 2-67 synthesis example

Sub 4-51 (CAS Registry Number: 2011776-79-5) (6.82 g, 18.84 mmol), Pd ₂ (dba) ₃ (0.47 g, 0.51 mmol) P( t -Bu) ₃ (0.21 g, 1.03 mmol), NaO t -Bu (4.94 g, 51.38 mmol), and toluene (180 ml) were added to obtain 10.36 g of product (yield) using the above 2-2 synthesis method : 79%) was obtained.

11. 2-73 synthesis example

Sub 4-53 (CAS Registry Number: 1646152-18-2) (10.30 g, 24.99 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.68 mmol) P( t -Bu) ₃ (0.28 g, 1.36 mmol), NaO t -Bu (6.55 g, 68.16 mmol), and toluene (240 ml) were added, and the product 12.61 g (yield) was obtained using the above 2-2 synthesis method : 68%) was obtained.

12. 2-84 synthesis example

Sub 4-37 (7.40 g, 20.50 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol) P( t -Bu) ₃ (0.23 g, 1.12 mmol), NaO t -Bu (5.37 g, 55.90 mmol), and toluene (195 ml) were added, and 12.40 g (yield: 87%) of the product was obtained using the above 2-2 synthesis method.

13. 2-112 synthesis example

Sub 4-68 (7.79 g, 22.85 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) P( t -Bu) ₃ (0.25 g, 1.25 mmol), NaO t -Bu (5.99 g, 62.32 mmol), and toluene (220 ml) were added, and 8.43 g (yield: 62%) of a product was obtained using the above 2-2 synthesis method.

14. 2-116 synthesis example

Sub 4-61 (CAS Registry Number: 29874-83-7) (5.51 g, 22.90 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) P( t -Bu) ₃ (0.25 g, 1.25 mmol), NaO t -Bu (6.00 g, 62.47 mmol), and toluene (220 ml) were added to obtain a product of 9.31 g (yield) using the above 2-2 synthesis method : 65%) was obtained.

15. 2-131 synthesis example

Sub 4-88 (10.75 g, 27.80 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.76 mmol) P( t -Bu) ₃ (0.31 g, 1.52 mmol), NaO t -Bu (7.29 g, 75.80 mmol), and toluene (265 ml) were added, and 12.73 g (yield: 72%) of a product was obtained using the above 2-2 synthesis method.

16. 2-133 synthesis example

Sub 4-46 (8.74 g, 22.57 mmol), Pd ₂ (dba) ₃ (0.56 g, 0.62 mmol) P( t -Bu) ₃ (0.25 g, 1.23 mmol), NaO t -Bu (5.92 g, 61.55 mmol), and toluene (215 ml) were added, and 10.11 g (yield: 77%) of the product was obtained using the above 2-2 synthesis method.

On the other hand, the FD-MS values of the compounds 2-1 to 2-135 of the present invention prepared according to the Synthesis Example as described above are shown in Table 3 below.

compound FD-MS compound FD-MS 2-1 m/z=636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-2 m/z=636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-3 m/z=649.25 (C ₄₈ H ₃₁ N ₃ =649.80) 2-4 m/z=639.24 (C ₄₅ H ₂₉ N ₅ =639.76) 2-5 m/z = 739.27 (C ₅₃ H ₃₃ N ₅ =739.88) 2-6 m/z=821.26 (C ₅₇ H ₃₅ N ₅ S=822.00) 2-7 m/z = 854.34 (C ₆₃ H ₄₂ N ₄ =855.06) 2-8 m/z = 909.33 (C ₆₅ H ₄₀ FN ₅ =910.07) 2-9 m/z = 728.27 (C ₅₁ H ₃₂ N ₆ =728.86) 2-10 m/z=612.23 (C ₄₄ H ₂₈ N ₄ =612.74) 2-11 m/z = 774.35 (C ₅₆ H ₂₂ D ₁₂ N ₄ =774.99) 2-12 m/z=908.26 (C ₆₄ H ₃₆ N ₄ OS=909.08) 2-13 m/z = 738.28 (C ₅₄ H ₃₄ N ₄ =738.89) 2-14 m/z=612.23 (C ₄₄ H ₂₈ N ₄ =612.74) 2-15 m/z = 738.28 (C ₅₄ H ₃₄ N ₄ =738.89) 2-16 m/z=868.27 (C ₆₂ H ₃₆ N ₄ S=869.06) 2-17 m/z = 738.28 (C ₅₄ H ₃₄ N ₄ =738.89) 2-18 m/z=854.30 (C ₆₂ H ₃₈ N ₄ O=855.01) 2-19 m/z=668.20 (C ₄₆ H ₂₈ N ₄ S=668.82) 2-20 m/z=794.25 (C ₅₆ H ₃₄ N ₄ S=794.98) 2-21 m/z = 845.32 (C ₆₀ H ₃₉ N ₅ O = 846.01) 2-22 m/z=749.27 (C ₅₂ H ₂₇ D ₅ N ₄ S=749.95) 2-23 m/z = 881.35 (C ₆₄ H ₄₃ N ₅ =882.08) 2-24 m/z=794.25 (C ₅₆ H ₃₄ N ₄ S=794.98) 2-25 m/z = 765.29 (C ₅₅ H ₃₅ N ₅ =765.92) 2-26 m/z = 874.33 (C ₆₇ H ₄₂ N ₂ =875.09) 2-27 m/z = 897.29 (C ₆₃ H ₃₉ N ₅ S = 898.10) 2-28 m/z=639.24 (C ₄₅ H ₂₉ N ₅ =639.76) 2-29 m/z = 815.30 (C ₅₉ H ₃₇ N ₅ =815.98) 2-30 m/z=863.30 (C ₆₃ H ₃₇ N ₅ =864.02) 2-31 m/z = 688.26 (C ₅₀ H ₃₂ N ₄ =688.83) 2-32 m/z=758.21 (C ₅₂ H ₃₀ N ₄ OS=758.90) 2-33 m/z=778.27 (C ₅₆ H ₃₄ N ₄ O=778.92) 2-34 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.86) 2-35 m/z = 924.30 (C ₆₄ H ₄₀ N ₆ S = 925.13) 2-36 m/z=844.32 (C ₆₁ H ₄₀ N ₄ O=845.02) 2-37 m/z = 882.41 (C ₆₂ H ₅₄ N ₄ Si = 883.23) 2-38 m/z = 736.29 (C ₅₆ H ₃₆ N ₂ =736.92) 2-39 m/z = 739.27 (C ₅₃ H ₃₃ N ₅ =739.88) 2-40 m/z=820.27 (C ₅₈ H ₃₆ N ₄ S=821.01) 2-41 m/z=839.30 (C ₆₁ H ₃₇ N ₅ =840.00) 2-42 m/z = 762.28 (C ₅₆ H ₃₄ N ₄ =762.92) 2-43 m/z=860.26 (C ₆₀ H ₃₆ N ₄ OS=861.04) 2-44 m/z=824.21 (C ₅₆ H ₃₂ N ₄ S2=825.02) 2-45 m/z = 786.30 (C ₆₀ H ₃₈ N ₂ =786.98) 2-46 m/z=689.26 (C ₄₉ H ₃₁ N ₅ =689.82) 2-47 m/z=850.31 (C ₆₃ H ₃₈ N ₄ =851.03) 2-48 m/z=855.30 (C ₆₁ H ₃₇ N ₅ O=856.00) 2-49 m/z=791.30 (C ₅₇ H ₃₇ N ₅ =791.96) 2-50 m/z=870.28 (C ₆₂ H ₃₈ N ₄ S=871.07) 2-51 m/z=839.30 (C ₆₁ H ₃₇ N ₅ =840.00) 2-52 m/z = 717.29 (C ₅₂ H ₂₇ D ₅ N ₄ =717.89) 2-53 m/z = 828.29 (C ₆₀ H ₃₆ N ₄ O = 828.98) 2-54 m/z = 867.34 (C ₆₃ H ₄₁ N ₅ =868.06) 2-55 m/z=828.33 (C ₆₁ H ₄₀ N ₄ =829.02) 2-56 m/z = 816.28 (C ₆₀ H ₃₆ N ₂ O ₂ =816.96) 2-57 m/z = 739.27 (C ₅₃ H ₃₃ N ₅ =739.88) 2-58 m/z = 890.34 (C ₆₆ H ₄₂ N ₄ =891.09) 2-59 m/z = 844.27 (C ₆₀ H ₃₆ N ₄ S = 845.04) 2-60 m/z = 702.24 (C ₅₀ H ₃₀ N ₄ O = 702.82) 2-61 m/z = 698.31 (C ₄₉ H ₂₂ D ₉ N ₅ =698.88) 2-62 m/z = 642.19 (C ₄₄ H ₂₆ N ₄ S = 642.78) 2-63 m/z=835.24 (C ₅₇ H ₃₃ N ₅ OS=835.99) 2-64 m/z = 826.22 (C ₅₆ H ₃₄ N ₄ S ₂ =827.04) 2-65 m/z=839.30 (C ₆₁ H ₃₇ N ₅ =840.00) 2-66 m/z=684.26 (C ₅₂ H ₃₂ N ₂ =684.84) 2-67 m/z = 765.29 (C ₅₅ H ₃₅ N ₅ =765.92) 2-68 m/z=654.22 (C ₄₆ H ₂₇ FN ₄ =654.75) 2-69 m/z=758.21 (C ₅₂ H ₃₀ N ₄ OS=758.90) 2-70 m/z = 855.34 (C ₆₂ H ₄₁ N ₅ =856.05) 2-71 m/z=684.26 (C ₅₂ H ₃₂ N ₂ =684.84) 2-72 m/z=778.27 (C ₅₆ H ₃₄ N ₄ O=778.92) 2-73 m/z = 815.30 (C ₅₉ H ₃₇ N ₅ =815.98) 2-74 m/z = 764.29 (C ₅₆ H ₃₆ N ₄ =764.93) 2-75 m/z=996.30 (C ₇₀ H ₄₀ N ₆ S=997.19) 2-76 m/z=560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 2-77 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.87) 2-78 m/z = 647.24 (C ₄₈ H ₂₉ N ₃ =647.78) 2-79 m/z = 814.31 (C ₆₀ H ₃₈ N ₄ =814.99) 2-80 m/z=790.31 (C ₅₈ H ₃₈ N ₄ =790.97) 2-81 m/z=639.24 (C ₄₅ H ₂₉ N ₅ =639.76) 2-82 m/z=801.37 (C ₅₇ H ₂₇ D ₁₀ N ₅ =802.02) 2-83 m/z=639.24 (C ₄₅ H ₂₉ N ₅ =639.76) 2-84 m/z = 764.29 (C ₅₆ H ₃₆ N ₄ =764.93) 2-85 m/z=830.28 (C ₅₈ H ₃₄ N ₆ O=830.95) 2-86 m/z = 738.28 (C ₅₄ H ₃₄ N ₄ =738.89) 2-87 m/z=612.23 (C ₄₄ H ₂₈ N ₄ =612.74) 2-88 m/z=712.26 (C ₅₂ H ₃₂ N ₄ =712.86) 2-89 m/z = 718.22 (C ₅₀ H ₃₀ N ₄ S = 718.88) 2-90 m/z = 764.29 (C ₅₆ H ₃₆ N ₄ =764.93) 2-91 m/z = 718.22 (C ₅₀ H ₃₀ N ₄ S = 718.88) 2-92 m/z = 844.27 (C ₆₀ H ₃₆ N ₄ S = 845.04) 2-93 m/z=892.28 (C ₆₄ H ₃₆ N ₄ O ₂ =893.02) 2-94 m/z=791.30 (C ₅₇ H ₃₇ N ₅ =791.96) 2-95 m/z=854.30 (C ₆₂ H ₃₈ N ₄ O=855.01) 2-96 m/z=690.25 (C ₄₈ H ₃₀ N ₆ =690.81) 2-97 m/z = 815.30 (C ₅₉ H ₃₇ N ₅ =815.98) 2-98 m/z = 893.33 (C ₆₃ H ₃₉ N ₇ =894.05) 2-99 m/z = 913.32 (C ₆₇ H ₃₉ N ₅ =914.08) 2-100 m/z = 930.37 (C ₆₉ H ₄₆ N ₄ =931.16) 2-101 m/z=501.16 (C ₃₆ H ₂₃ NS=501.65) 2-102 m/z=580.17 (C ₃₉ H ₂₄ N ₄ S=580.71) 2-103 m/z=643.17 (C _{4 4} H ₂₅ N ₃ OS=643.76) 2-104 m/z=838.31 (C ₆₂ H ₃₈ N ₄ =839.01) 2-105 m/z = 779.26 (C ₅₆ H ₃₃ N ₃ O ₂ =779.90) 2-106 m/z=709.28 (C ₅₅ H ₃₅ N=709.89) 2-107 m/z=685.16 (C ₄₆ H ₂₇ N ₃ S ₂ =685.86) 2-108 m/z=577.18 (C ₄₀ H ₂₃ N ₃ O ₂ =577.64) 2-109 m/z = 738.19 (C ₄₉ H ₃₀ N ₄ S ₂ =738.93) 2-110 m/z=662.25 (C ₄₈ H ₃₀ N ₄ =662.80) 2-111 m/z = 630.19 (C ₄₃ H ₂₆ N ₄ S = 630.77) 2-112 m/z=654.19 (C ₄₅ H ₂₆ N ₄ S=654.79) 2-113 m/z=737.25 (C ₅₄ H ₃₁ N ₃ O=737.86) 2-114 m/z = 775.21 (C ₅₃ H ₃₃ N ₃ S ₂ =775.99) 2-115 m/z=561.21 (C ₄₂ H ₂₇ NO=561.68) 2-116 m/z = 687.27 (C ₅₁ H ₃₃ N ₃ =687.85) 2-117 m/z=720.20 (C ₄₉ H ₂₈ N ₄ OS=720.85) 2-118 m/z=579.18 (C ₄₀ H ₂₅ N ₃ S=579.72) 2-119 m/z = 912.33 (C ₆₈ H ₄₀ N ₄ =913.10) 2-120 m/z = 677.25 (C ₄₉ H ₃₁ N ₃ O = 677.81) 2-121 m/z=664.23 (C ₄₇ H ₂₈ N ₄ O=664.77) 2-122 m/z=755.24 (C ₅₄ H ₃₃ N ₃ S=755.94) 2-123 m/z=653.25 (C ₄₇ H ₃₁ N ₃ O=653.79) 2-124 m/z=589.23 (C ₃₉ H ₁₅ D ₉ N ₄ S=589.76) 2-125 m/z=517.12 (C ₃₄ H ₁₉ N ₃ OS=517.61) 2-126 m/z=549.16 (C ₄₀ H ₂₃ NS=549.69) 2-127 m/z=614.21 (C ₄₃ H ₂₆ N ₄ O=614.71) 2-128 m/z=595.15 (C ₄₀ H ₂₂ FN ₃ S=595.70) 2-129 m/z=729.28 (C53H35N3O=729.88) 2-130 m/z=819.23 (C ₅₈ H ₃₃ N ₃ OS=819.98) 2-131 m/z=699.14 (C ₄₆ H ₂₅ N ₃ OS ₂ =699.85) 2-132 m/z=739.30 (C ₅₅ H ₃₇ N ₃ =739.92) 2-133 m/z = 639.23 (C ₄₆ H ₂₉ N 3 O = 639.76) 2-134 m/z=732.23 (C ₅₁ H ₃₂ N ₄ S=732.91) 2-135 m/z = 777.28 (C ₅₇ H ₃₅ N ₃ O = 777.93)

Meanwhile, although exemplary synthesis examples of the present invention represented by Formula 1 and Formula 2 have been described above, they are all Buchwald-Hartwig cross coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, intramolecular acid-induced cyclization reaction ( J Mater. Chem . 1999, 9 , 2095.), Pd(II)-catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13 , 5504) and PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70 , 5014.) and the like, in addition to the substituents specified in the specific synthesis examples, other substituents defined in Formula 1 and Formula 2 (X ¹ to X ³ , L ¹ to L ⁸ , Ar ¹ to Ar ⁸ , A, B, C, Substituents such as D, E, F, G and H) are bonded, it will be easily understood by those skilled in the art that the above reaction proceeds.

Manufacturing evaluation of organic electric devices

[ Example 1] to [ Example 158] red organic light emitting device ( light emitting layer mixed phosphorescent host)

First, on the ITO layer (anode) formed on the glass substrate, a 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (abbreviated as 2-TNATA) film was vacuum-deposited as a hole injection layer to form a 60 nm Next, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was vacuum deposited to a thickness of 60 nm to form a hole transport layer.The compound of the present invention represented by Formula 1 (first host) and Formula 2 (second host) (listed in Table 4) was used as a host on the top of the hole transport layer 3: 7 was used, and as a dopant, (piq) ₂ Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was doped with 5% weight to form a light emitting layer having a thickness of 30 nm on the hole transport layer. As a hole-blocking layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm. , Bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq ₂ ) was deposited with a thickness of 50 nm as an electron transport layer, and LiF, an alkali metal halide, was deposited with a thickness of 0.2 nm as an electron injection layer. Then, an organic light emitting device was manufactured by depositing Al to a thickness of 150 nm and using it as a cathode.

[ comparative example 1] to [ comparative example 3]

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention represented by Formula 2 (listed in Table 4) was used alone as a host.

[ comparative example 4]

An organic light emitting device was manufactured in the same manner as in Example 1, except that Comparative Compound v1 and Compounds 2-4 of the present invention were mixed and used as a host.

Electroluminescence (EL) characteristics with PR-650 of Photoresearch Co., Ltd. by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 158 and Comparative Examples 1 to 4 of the present invention was measured, and the T95 life was measured through McScience's life measurement equipment at 2500 cd / m ² standard luminance, and the measurement results are shown in Table 4 below.

1st host 2nd host drive voltage
(V) electric current
(mA/cm ² ) luminance
(cd/m ² ) efficiency
(cd/A) life span
T(95) CIE x y Comparative Example (1) - 2-1 6.9 21.9 2500 11.4 73.9 0.67 0.32 Comparative example (2) - 2-4 5.8 19.7 2500 12.7 98.4 0.66 0.34 Comparative Example (3) - 2-111 6.0 20.7 2500 12.1 87.2 0.66 0.33 Comparative example (4) v1 2-4 5.8 18.7 2500 13.3 95.5 0.66 0.34 Example (1) 1-1 2-4 5.3 7.8 2500 32.1 139.4 0.66 0.35 Example (2) 1-16 2-4 5.1 7.3 2500 34.5 144.8 0.66 0.34 Example (3) 1-53 2-4 5.1 7.9 2500 31.6 140.0 0.66 0.35 Example (4) 1-59 2-4 5.0 7.1 2500 35.0 145.5 0.66 0.35 Example (5) 1-65 2-4 5.1 7.6 2500 32.8 139.4 0.66 0.35 Example (6) 1-66 2-4 5.0 7.3 2500 34.1 144.7 0.66 0.35 Example (7) 1-76 2-4 5.0 7.3 2500 34.5 144.9 0.66 0.34 Example (8) 1-116 2-4 5.1 7.8 2500 31.9 139.4 0.66 0.34 Example (9) 1-117 2-4 5.3 7.8 2500 32.2 139.8 0.66 0.34 Example (10) 1-119 2-4 5.2 8.2 2500 30.7 138.4 0.66 0.35 Example (11) 1-125 2-4 5.2 8.2 2500 30.7 138.3 0.66 0.35 Example (12) 1-139 2-4 5.2 7.7 2500 32.5 140.0 0.66 0.34 Example (13) 1-182 2-4 5.1 7.5 2500 33.4 140.6 0.66 0.34 Example (14) 1-186 2-4 5.3 7.4 2500 33.6 142.8 0.66 0.34 Example (15) 1-188 2-4 5.2 7.6 2500 32.8 139.9 0.66 0.34 Example (16) 1-190 2-4 5.1 7.6 2500 32.8 139.8 0.66 0.35 Example (17) 1-195 2-4 5.2 7.9 2500 31.7 139.7 0.66 0.34 Example (18) 1-201 2-4 5.2 7.9 2500 31.5 139.4 0.66 0.34 Example (19) 1-205 2-4 5.2 8.1 2500 30.8 138.4 0.66 0.35 Example (20) 1-258 2-4 5.3 8.1 2500 30.8 138.1 0.66 0.35 Example (21) 1-1 2-10 5.3 9.2 2500 27.2 134.0 0.66 0.35 Example (22) 1-16 2-10 5.2 8.8 2500 28.4 136.5 0.66 0.35 Example (23) 1-53 2-10 5.3 9.2 2500 27.2 134.2 0.66 0.35 Example (24) 1-59 2-10 5.2 8.6 2500 29.1 138.3 0.66 0.34 Example (25) 1-65 2-10 5.3 9.1 2500 27.4 134.6 0.66 0.34 Example (26) 1-66 2-10 5.3 8.8 2500 28.3 136.1 0.66 0.35 Example (27) 1-76 2-10 5.2 8.7 2500 28.6 137.9 0.66 0.34 Example (28) 1-116 2-10 5.3 9.2 2500 27.0 134.1 0.66 0.34 Example (29) 1-117 2-10 5.3 9.2 2500 27.1 134.2 0.66 0.35 Example (30) 1-119 2-10 5.3 9.4 2500 26.6 133.5 0.66 0.35 Example (31) 1-125 2-10 5.3 9.3 2500 26.7 133.6 0.66 0.35 Example (32) 1-139 2-10 5.3 9.1 2500 27.5 134.4 0.66 0.35 Example (33) 1-182 2-10 5.3 9.0 2500 27.8 135.8 0.66 0.35 Example (34) 1-186 2-10 5.4 8.9 2500 27.9 135.2 0.66 0.34 Example (35) 1-188 2-10 5.3 9.1 2500 27.4 135.4 0.66 0.35 Example (36) 1-190 2-10 5.3 9.1 2500 27.5 134.8 0.66 0.34 Example (37) 1-195 2-10 5.4 9.2 2500 27.1 134.2 0.66 0.34 Example (38) 1-201 2-10 5.3 9.2 2500 27.1 134.0 0.66 0.34 Example (39) 1-205 2-10 5.3 9.4 2500 26.6 133.5 0.66 0.35 Example (40) 1-258 2-10 5.3 9.3 2500 26.9 133.0 0.66 0.34 Example (41) 1-1 2-15 5.3 8.8 2500 28.3 136.7 0.66 0.34 Example (42) 1-16 2-15 5.2 7.8 2500 31.9 139.2 0.66 0.34 Example (43) 1-53 2-15 5.3 8.8 2500 28.5 137.1 0.66 0.35 Example (44) 1-59 2-15 5.1 7.6 2500 32.8 139.3 0.66 0.34 Example (45) 1-65 2-15 5.2 8.6 2500 29.1 136.5 0.66 0.34 Example (46) 1-66 2-15 5.2 8.1 2500 30.7 138.1 0.66 0.34 Example (47) 1-76 2-15 5.2 8.0 2500 31.4 139.6 0.66 0.35 Example (48) 1-116 2-15 5.3 8.7 2500 28.7 136.2 0.66 0.34 Example (49) 1-117 2-15 5.3 8.8 2500 28.5 137.1 0.66 0.35 Example (50) 1-119 2-15 5.3 8.9 2500 28.2 136.4 0.66 0.35 Example (51) 1-125 2-15 5.4 8.9 2500 28.2 136.5 0.66 0.34 Example (52) 1-139 2-15 5.2 8.6 2500 29.2 137.7 0.66 0.34 Example (53) 1-182 2-15 5.2 8.5 2500 29.5 137.4 0.66 0.34 Example (54) 1-186 2-15 5.2 8.4 2500 29.7 136.6 0.66 0.35 Example (55) 1-188 2-15 5.2 8.6 2500 29.2 136.9 0.66 0.35 Example (56) 1-190 2-15 5.2 8.6 2500 29.2 137.0 0.66 0.34 Example (57) 1-195 2-15 5.3 8.7 2500 28.6 136.2 0.66 0.34 Example (58) 1-201 2-15 5.2 8.8 2500 28.4 137.4 0.66 0.34 Example (59) 1-205 2-15 5.2 8.9 2500 28.1 136.2 0.66 0.35 Example (60) 1-258 2-15 5.2 8.9 2500 28.2 136.3 0.66 0.35 Example (61) 1-1 2-19 5.4 9.2 2500 27.1 133.9 0.66 0.35 Example (62) 1-16 2-19 5.3 8.8 2500 28.5 136.7 0.66 0.35 Example (63) 1-53 2-19 5.2 9.2 2500 27.2 134.0 0.66 0.34 Example (64) 1-59 2-19 5.2 8.6 2500 29.1 138.3 0.66 0.35 Example (65) 1-65 2-19 5.2 9.1 2500 27.4 134.5 0.66 0.34 Example (66) 1-66 2-19 5.2 8.8 2500 28.3 136.3 0.66 0.35 Example (67) 1-76 2-19 5.3 8.8 2500 28.4 136.6 0.66 0.35 Example (68) 1-116 2-19 5.2 9.2 2500 27.1 133.9 0.66 0.34 Example (69) 1-117 2-19 5.3 9.2 2500 27.1 133.8 0.66 0.34 Example (70) 1-119 2-19 5.3 9.4 2500 26.7 133.6 0.66 0.35 Example (71) 1-125 2-19 5.3 9.3 2500 26.9 133.7 0.66 0.35 Example (72) 1-139 2-19 5.2 9.1 2500 27.4 134.9 0.66 0.35 Example (73) 1-182 2-19 5.4 8.9 2500 28.0 135.1 0.66 0.35 Example (74) 1-186 2-19 5.4 9.0 2500 27.8 134.7 0.66 0.34 Example (75) 1-188 2-19 5.4 9.1 2500 27.4 134.7 0.66 0.34 Example (76) 1-190 2-19 5.2 9.1 2500 27.4 134.3 0.66 0.34 Example (77) 1-195 2-19 5.3 9.2 2500 27.2 134.1 0.66 0.34 Example (78) 1-201 2-19 5.3 9.2 2500 27.3 133.9 0.66 0.34 Example (79) 1-205 2-19 5.3 9.3 2500 27.0 133.5 0.66 0.35 Example (80) 1-258 2-19 5.3 9.3 2500 26.9 133.6 0.66 0.35 Example (81) 1-16 2-28 5.2 9.7 2500 25.7 131.9 0.66 0.35 Example (82) 1-59 2-28 5.3 9.6 2500 25.9 132.7 0.66 0.34 Example (83) 1-65 2-28 5.4 10.0 2500 24.9 130.6 0.66 0.34 Example (84) 1-66 2-28 5.4 9.9 2500 25.2 131.2 0.66 0.34 Example (85) 1-76 2-28 5.4 9.8 2500 25.6 132.7 0.66 0.35 Example (86) 1-139 2-28 5.4 10.1 2500 24.8 130.1 0.66 0.34 Example (87) 1-182 2-28 5.4 10.0 2500 25.0 130.9 0.66 0.35 Example (88) 1-186 2-28 5.5 10.0 2500 25.0 130.2 0.66 0.35 Example (89) 1-188 2-28 5.5 10.1 2500 24.8 130.7 0.66 0.34 Example (90) 1-190 2-28 5.4 10.1 2500 24.8 130.2 0.66 0.35 Example (91) 1-16 2-46 5.3 9.8 2500 25.6 132.6 0.66 0.34 Example (92) 1-59 2-46 5.4 9.7 2500 25.9 132.6 0.66 0.34 Example (93) 1-65 2-46 5.5 10.1 2500 24.9 130.6 0.66 0.34 Example (94) 1-66 2-46 5.4 9.9 2500 25.3 131.6 0.66 0.34 Example (95) 1-76 2-46 5.3 9.8 2500 25.6 132.4 0.66 0.34 Example (96) 1-139 2-46 5.4 10.1 2500 24.8 130.5 0.66 0.34 Example (97) 1-182 2-46 5.4 10.0 2500 25.1 130.4 0.66 0.35 Example (98) 1-186 2-46 5.5 10.0 2500 25.0 130.1 0.66 0.34 Example (99) 1-188 2-46 5.4 10.1 2500 24.8 130.1 0.66 0.35 Example (100) 1-190 2-46 5.4 10.1 2500 24.8 130.5 0.66 0.35 Example (101) 1-16 2-74 5.3 9.8 2500 25.5 131.9 0.66 0.35 Example (102) 1-59 2-74 5.3 9.6 2500 25.9 132.8 0.66 0.34 Example (103) 1-65 2-74 5.5 10.1 2500 24.8 130.4 0.66 0.34 Example (104) 1-66 2-74 5.3 9.9 2500 25.3 131.1 0.66 0.35 Example (105) 1-76 2-74 5.2 9.8 2500 25.4 131.8 0.66 0.35 Example (106) 1-139 2-74 5.4 10.1 2500 24.9 130.8 0.66 0.35 Example (107) 1-182 2-74 5.5 10.0 2500 25.0 130.9 0.66 0.35 Example (108) 1-186 2-74 5.4 10.0 2500 25.1 130.8 0.66 0.34 Example (109) 1-188 2-74 5.5 10.1 2500 24.8 131.0 0.66 0.34 Example (110) 1-190 2-74 5.4 10.1 2500 24.9 130.5 0.66 0.34 Example (111) 1-1 2-81 5.3 9.8 2500 25.5 131.8 0.66 0.34 Example (112) 1-16 2-81 5.2 9.2 2500 27.2 134.1 0.66 0.34 Example (113) 1-53 2-81 5.3 9.8 2500 25.5 131.7 0.66 0.34 Example (114) 1-59 2-81 5.2 9.1 2500 27.4 134.5 0.66 0.34 Example (115) 1-65 2-81 5.4 9.6 2500 26.0 132.2 0.66 0.34 Example (116) 1-66 2-81 5.2 9.4 2500 26.7 133.6 0.66 0.35 Example (117) 1-76 2-81 5.3 9.2 2500 27.2 134.1 0.66 0.35 Example (118) 1-116 2-81 5.3 9.8 2500 25.5 131.7 0.66 0.35 Example (119) 1-117 2-81 5.3 9.7 2500 25.7 131.7 0.66 0.35 Example (120) 1-139 2-81 5.2 9.6 2500 25.9 132.5 0.66 0.35 Example (121) 1-182 2-81 5.2 9.5 2500 26.3 131.9 0.66 0.35 Example (122) 1-186 2-81 5.2 9.5 2500 26.4 131.7 0.66 0.34 Example (123) 1-188 2-81 5.4 9.7 2500 25.9 132.5 0.66 0.34 Example (124) 1-190 2-81 5.3 9.6 2500 25.9 132.1 0.66 0.34 Example (125) 1-195 2-81 5.3 9.8 2500 25.6 132.7 0.66 0.35 Example (126) 1-201 2-81 5.4 9.8 2500 25.5 131.7 0.66 0.34 Example (127) 1-1 2-83 5.3 9.8 2500 25.5 132.8 0.66 0.34 Example (128) 1-16 2-83 5.3 9.2 2500 27.3 133.8 0.66 0.35 Example (129) 1-53 2-83 5.3 9.8 2500 25.4 132.3 0.66 0.35 Example (130) 1-59 2-83 5.3 9.1 2500 27.4 134.3 0.66 0.34 Example (131) 1-65 2-83 5.3 9.7 2500 25.9 131.8 0.66 0.35 Example (132) 1-66 2-83 5.2 9.3 2500 26.8 133.2 0.66 0.35 Example (133) 1-76 2-83 5.3 9.2 2500 27.2 134.0 0.66 0.35 Example (134) 1-116 2-83 5.2 9.8 2500 25.5 131.9 0.66 0.34 Example (135) 1-117 2-83 5.3 9.8 2500 25.5 132.7 0.66 0.34 Example (136) 1-139 2-83 5.3 9.7 2500 25.9 132.7 0.66 0.35 Example (137) 1-182 2-83 5.2 9.5 2500 26.4 132.4 0.66 0.34 Example (138) 1-186 2-83 5.3 9.5 2500 26.3 131.9 0.66 0.35 Example (139) 1-188 2-83 5.3 9.7 2500 25.8 132.3 0.66 0.34 Example (140) 1-190 2-83 5.2 9.6 2500 25.9 132.0 0.66 0.35 Example (141) 1-195 2-83 5.2 9.8 2500 25.5 132.8 0.66 0.34 Example (142) 1-201 2-83 5.3 9.8 2500 25.5 132.2 0.66 0.34 Example (143) 1-1 2-111 5.3 9.7 2500 25.7 131.8 0.66 0.35 Example (144) 1-16 2-111 5.3 9.2 2500 27.2 134.1 0.66 0.34 Example (145) 1-53 2-111 5.4 9.8 2500 25.5 132.1 0.66 0.35 Example (146) 1-59 2-111 5.3 9.1 2500 27.5 135.3 0.66 0.34 Example (147) 1-65 2-111 5.4 9.6 2500 26.0 131.8 0.66 0.35 Example (148) 1-66 2-111 5.4 9.3 2500 26.8 133.6 0.66 0.34 Example (149) 1-76 2-111 5.4 9.2 2500 27.2 133.8 0.66 0.34 Example (150) 1-116 2-111 5.4 9.8 2500 25.6 131.8 0.66 0.34 Example (151) 1-117 2-111 5.3 9.8 2500 25.6 132.2 0.66 0.35 Example (152) 1-139 2-111 5.3 9.7 2500 25.9 132.2 0.66 0.34 Example (153) 1-182 2-111 5.3 9.5 2500 26.4 132.5 0.66 0.35 Example (154) 1-186 2-111 5.4 9.5 2500 26.4 132.0 0.66 0.34 Example (155) 1-188 2-111 5.4 9.7 2500 25.9 131.6 0.66 0.34 Example (156) 1-190 2-111 5.3 9.7 2500 25.9 132.4 0.66 0.35 Example (157) 1-195 2-111 5.2 9.7 2500 25.7 132.6 0.66 0.35 Example (158) 1-201 2-111 5.2 9.8 2500 25.5 131.8 0.66 0.35

As can be seen from the results of Table 4, when the organic electroluminescent device materials of the present invention represented by Formulas 1 and 2 are mixed and used as a phosphorescent host (Examples 1 to 158), a device using a single material (Comparative Example 1 to Comparative Example 3) or by mixing the comparative compound v1 and the compound 2-4 of the present invention, it can be seen that the driving voltage, efficiency and lifetime are significantly improved compared to the device used as a phosphorescent host (Comparative Example 4).

In particular, it can be confirmed that Comparative Example 4 using a mixture of Comparative Compound v1 and Compounds 2-4 of the present invention as a phosphorescent host exhibits higher efficiency than Comparative Examples 1 to 3 using a single material. Comparative Example 4 It can be seen that Examples 1 to 158 in which the compounds of Formula 1 and Formula 2, which are compounds of the present invention, are mixed and used as hosts, exhibit significantly higher efficiency and lifespan than in the case of .

Based on the above experimental results, the present inventors have determined that a mixture of the material of Formula 1 and the material of Formula 2 has novel properties other than the properties of each material, and the material of Formula 1 and the material of Formula 2 , PL lifetime was measured using each of the mixtures of the present invention. As a result, it was confirmed that when the compounds of the present invention, Formula 1 and Formula 2 were mixed, a new PL wavelength was formed, unlike the case of a single compound, and the reduction and extinction time of the newly formed PL wavelength was It was confirmed that the decrease and disappearance time increased from about 60 times to about 360 times. This is because when the compounds of the present invention are mixed and used, electrons and holes move through the energy levels of each material, as well as electrons and holes move or energy by new exciplexes with new energy levels formed by mixing. It is judged that the efficiency and lifetime increase with the transfer. As a result, when the mixture of the present invention is used, it can be said that the mixed thin film shows an exciplex energy transfer and light emission process.

In addition, the reason why the combination of the present invention is excellent is that when a compound represented by Chemical Formula 1 having strong hole characteristics is mixed with a bis-type heterocyclic compound represented by Chemical Formula 2, which has stability for electrons as well as holes and high T1, etc. , due to the high T1 and high LUMO energy value, the electron blocking ability is improved, and more holes in the light emitting layer move quickly and easily. As a result, the charge balance of holes and electrons in the light emitting layer is increased, so that light is emitted well inside the light emitting layer, not at the interface of the hole transport layer, and as a result, deterioration at the HTL interface is also reduced, and it is judged that the driving voltage, efficiency, and lifespan of the entire device are maximized. . That is, in conclusion, it is considered that the combination of Chemical Formulas 1 and 2 has a synergistic effect electrochemically to improve the performance of the entire device.

[ Example 159] to [ Example 161] by mixing ratio red organic light emitting device ( light emitting layer mixed phosphorescent host)

As shown in Table 5, an organic light emitting device was manufactured in the same manner as in Example 4, except that different mixing ratios of materials were used.

[ Example 162] to [ Example 164] by mixing ratio red organic light emitting device ( light emitting layer mixed phosphorescent host)

As shown in Table 5, an organic light emitting device was manufactured in the same manner as in Example 153, except that different mixing costs were used.

Electroluminescence (EL) characteristics of PR-650 manufactured by Photoresearch Co., Ltd. by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Example 4, Example 153, and Example 159 to Example 164 of the present invention was measured, and the T95 life was measured through McScience's life measurement equipment at 2500 cd / m ² standard luminance, and the measurement results are shown in Table 5 below.

1st host 2nd host mixing ratio
(First host:
2nd host) Driving
Voltage
(V) electric current
(mA/cm ² ) luminance
(cd/m ² ) efficiency
(cd/A) life span
T(95) CIE x y Example (159) 1-59 2-4 2:8 5.1 7.2 2500 34.6 144.1 0.66 0.35 Example (4) 1-59 2-4 3:7 5.0 7.1 2500 35.0 145.5 0.66 0.35 Example (160) 1-59 2-4 4:6 5.4 7.5 2500 33.4 138.0 0.66 0.35 Example (161) 1-59 2-4 5:5 5.6 8.0 2500 31.2 130.3 0.66 0.35 Example (162) 1-182 2-111 2:8 5.3 9.3 2500 26.9 133.1 0.66 0.35 Example (153) 1-182 2-111 3:7 5.3 9.5 2500 26.4 132.5 0.66 0.35 Example (163) 1-182 2-111 4:6 5.5 10.1 2500 24.8 129.4 0.66 0.35 Example (164) 1-182 2-111 5:5 5.8 10.9 2500 23.0 123.6 0.66 0.35

As shown in Table 5, a mixture of the compounds of the present invention was prepared and measured by ratio (2:8, 3:7, 4:6, 5:5). In the results of the mixture of compound 1-59 and compound 2-4, the results of driving voltage, efficiency and life were similarly excellent when mixed at 2:8 and 3:7, but in the case of mixing ratios of 4:6 and 5:5 As the ratio of the first host increases, it can be seen that the results of driving voltage, efficiency, and lifespan gradually decrease. These results showed the same pattern when compound 1-182 and compound 2-111 were mixed. It is believed that this is because the charge balance in the light emitting layer is maximized when an appropriate amount of the compound represented by Chemical Formula 1 having strong hole characteristics, such as 2:8 and 3:7, is mixed.

The above description is only illustrative 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. Therefore, the embodiments disclosed in this specification are intended to explain the present invention, not to limit it, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed according to the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

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

Claims (15)

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

{In Formula 1, Formula 1-1 and Formula 2,
M is a C ₆ -C ₆₀ arylene group or Formula 1-1;
X ¹ is S or O;
X ² is NL ⁵ -Ar ⁶ , O, S or CR ^a R ^b ;
X ³ is NL ⁸ -Ar ⁸ , O, S or CR ^c R ^d ;
A, B, C, D, E, F, G and H are each independently a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heterocyclic group,
C is bonded to L ³ , D is bonded to L ⁴ ,
R ^a , R ^b , R ^c and R ^d are each independently hydrogen, deuterium; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; And a C ₂ -C ₂₀ alkenyl group; is selected from the group consisting of, R ^a and R ^b may bond to each other to form a spiro compound,
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ may each independently represent a C ₆ -C ₆₀ aryl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; And a C ₆ -C ₆₀ aromatic ring and C ₃ -C ₆₀ fused ring group of an aliphatic ring; is selected from the group consisting of;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ may each independently be a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And it is selected from the group consisting of an aliphatic hydrocarbon group,
Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group and alkenyl group are each deuterium; halogen; silane group; cyano group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; A C ₇ -C ₂₀ arylalkyl group and a 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 combine with each other to form a ring, where ' The term 'ring' refers to a C ₃ -C ₆₀ aliphatic ring, C ₆ -C ₆₀ aromatic ring, C ₂ -C ₆₀ hetero ring, or a fused ring composed of a combination thereof, and includes a saturated or unsaturated ring.}
The method of claim 1, wherein in Formula 1, Formula 1-1 or 2, A, B, C, D, E, and F are each independently selected from the group consisting of Formulas a-1 to Formulas a-7 An organic electric element, characterized in that any one.

{In the formula a-1 to formula a-7,
Z ¹ to Z ⁴⁸ are CR ^e or N;
However, Z ¹ to Z ⁴⁸ bonded to L ¹ to L ⁶ are carbon (C),
R ^e is the same as the definition of R ^a in claim 1 above;
* indicates the condensed position.}
The organic electric device according to claim 1, wherein in Formula 1, Formula 1-1 or Formula 2, L ¹ to L ⁶ are compounds represented by any one of Formulas b-1 to b-13 below.

Formula b-11 Formula b-12 Formula b-13

{In the formula b-1 to formula b-13,
Y is NL ⁹ -Ar ⁹ , O, S or CR ^f R ^g ;
L ⁹ is the same as the definition of L ⁵ in Claim 1 above;
Ar ⁹ is the same as the definition of Ar ⁶ in claim 1,
R ^f and R ^g are the same as the definition of R ^a in claim 1 above,
a, c, d, e are each independently an integer from 0 to 4, b is an integer from 0 to 6, f and g are independently an integer from 0 to 3, h is an integer from 0 to 2, i is an integer of 0 or 1;
R ¹ to R ³ are each independently hydrogen; heavy hydrogen; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; And C ₂ -C ₂₀ alkenyl group; is selected from the group consisting of, or when a, b, c, d, e, f and g are 2 or more, and when h is 2, each is plural and the same as each other, or Different and a plurality of R ¹ , a plurality of R ² , or a plurality of R ³ , or adjacent R ¹ and R ² or R ² and R ³ may bond to each other to form an aromatic ring or a heteroaromatic ring,
Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ are independently CR ^j or N, and at least one of Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ is N,
R ^j is hydrogen; heavy hydrogen; tritium; halogen; cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; And a C ₂ -C ₂₀ alkenyl group; selected from the group consisting of, and adjacent R ¹ and R ^h may combine with each other to form an aromatic ring or a heteroaromatic ring.}
The organic electric device according to claim 1, wherein at least one of Ar ¹ to Ar ⁵ in Chemical Formula 1 is represented by Chemical Formula 1-2 below.

{In Formula 1-2,
I and J are the same as the definition of A in claim 1,
X ⁴ is NL ¹¹ -Ar ¹⁰ , O, S or CR ^k R ^l ;
L ¹⁰ and L ¹¹ are the same as the definition of L ⁵ in claim 1,
Ar ¹⁰ is the same as the definition of Ar ⁶ in claim 1,
R ^k and R ^l have the same definition as R ^a in claim 1 above.}
The organic electric device according to claim 4, wherein the first host compound represented by Chemical Formula 1 is represented by Chemical Formula 3 below.

{In Formula 3,
X ¹ , X ² , Ar ¹ to Ar ⁵ are as defined in claim 1 above,
Z ¹ to Z ⁴ are independently of each other CR ^e or N;
However, Z ¹ to Z ⁴ bonded to N are carbon (C),
R ^e is the same as the definition of R ^a in claim 1}
The organic electric device according to claim 1, wherein X ¹ and X ² in Chemical Formula 1 are independently O or S.
The organic electric device according to claim 1, wherein the second host compound represented by Chemical Formula 2 is represented by any one of Chemical Formulas 4 to 7 below.

{In Formula 4 to Formula 7,
E, F, G, H, L ⁶ , L ⁷ , L ⁸ , Ar ⁷ , Ar ⁸ , R ^c , R ^d are as defined in claim 1 above.}
The organic electric device according to claim 1, wherein the first host compound represented by Chemical Formula 1 is any one of the following compounds 1-1 to 1-265.

The organic electric device according to claim 1, wherein the second host compound represented by Chemical Formula 2 is any one of the following compounds 2-1 to 2-135.

The method of claim 1, wherein one or more hole transport band layers are included between the first electrode and the light emitting layer, the hole transport band layer includes a hole transport layer, a light emitting auxiliary layer, or both, and the hole transport band layer is An organic electric device comprising the compound represented by Formula 1 above.
The organic electric device according to claim 1, wherein the compounds represented by Chemical Formula 1 and Chemical Formula 2 are mixed in a weight ratio of 1:9 to 9:1 and included in the light emitting layer.
The organic electric device according to claim 1, wherein the compounds represented by Chemical Formulas 1 and 2 are mixed in a weight ratio of 1:9 to 5:5 and included in the light emitting layer.
The organic electric device according to claim 1, wherein the compounds represented by Chemical Formulas 1 and 2 are mixed at a weight ratio of 2:8 or 3:7 and included in the light emitting layer.
An electronic device comprising: a display device including the organic electric element of claim 1; and a control unit driving the display device.
15. The electronic device according to claim 14, wherein the organic electric device is any one of an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white light device.

Images