KR102429424B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

By using the mixture of the compounds according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electrical device, and to provide an organic electrical device and an electronic device capable of greatly improving the lifespan of the device. to provide.

Description

Compound for organic electric device, organic electric device using 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 electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multi-layered 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.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, according to their function.

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

As a representative example, the following Patent Documents 1 to 4 report performance according to hetero type and arrangement, substituent type, fused position, etc. for a 5-cyclic cyclic compound among polycyclic cyclic compounds.

[Patent Document 1]: US Patent 5843607

[Patent Document 2]: Japanese Patent Application Laid-Open No. 1999-162650

[Patent Document 3] : Korean Patent Publication 2008-0085000

[Patent Document 4]: US Patent Publication 2010-0187977

[Patent Document 5] : Korean Patent Publication 2011-0018340

[Patent Document 6] : Korean Patent Publication 2009-0057711

Patent Document 1 and Patent Document 2 report examples in which an indolocarbazole core composed of only nitrogen (N) as a hetero atom in a 5-ring cyclic compound is used, and an aryl group substituted or unsubstituted for N of indolocarbazole is used. have. However, in the case of Prior Invention 1, there is only a simple aryl group in which an alkyl group, an amino group, an alkoxy group, etc. are substituted or unsubstituted as a substituent. , their use as phosphorescent host materials has not been described.

Patent Document 3 and Patent Document 4 include pyridine, pyrimidine, triazine, etc. each containing an aryl group and N in the indolocarbazole four core having a heteroatom of N in the same 5-cyclic cyclic compound as in Patent Document 1 and Patent Document 2, respectively. Although substituted compounds are described, only examples of use for phosphorescent green host materials are described, and performance for other heterocyclic compounds substituted on the indolocarbazole core is not described.

In Patent Document 5, nitrogen (N), oxygen (O), sulfur (S), carbon, etc. are described as heteroatoms in the five-ring cyclic compound, but only examples using identical heteroatoms exist in the performance measurement data. , it was not possible to confirm the performance characteristics of the five-ring cyclic compound containing a heteroatom.

Therefore, in the above patent document, a solution to the low charge carrier mobility and low oxidation stability of the five-ring cyclic compound containing the isotype heteroatom is not described.

When pentacyclic cyclic compound molecules are generally stacked, a strong electrical interaction occurs as the number of adjacent π-electrons increases, which is closely related to charge carrier mobility. When is stacked, the arrangement order between molecules takes an edge-to-face form, whereas in a heterocyclic five-ring compound with different heteroatoms, the packing structure of the molecule faces in the opposite direction (antiparallelcofacial π-stacking). structure), so that the arrangement order between molecules has a face-to-face form. At the asymmetrically arranged heteroatom N, which is the cause of this layered structure, It has been reported that relatively high carrier mobility and high oxidation stability are caused due to the steric effect of the substituents being substituted. ( Org . Lett . 2008, 10 , 1199)

In Patent Document 6, examples of using as a fluorescent host material for various polycyclic compounds having 7 or more rings have been reported.

As described above, the fused position, number of rings, arrangement of heteroatoms, and property changes according to types of polycyclic cyclic compounds have not yet been sufficiently developed.

In particular, in a phosphorescent organic electric device using a phosphorescent light emitting dopant material, the LUIMO and HOMO levels of the host material are factors that greatly affect the efficiency and lifespan of the organic electric device, and it is possible to efficiently control electron and hole injection in the light emitting layer This is because it is possible to prevent a decrease in efficiency and a decrease in lifespan due to the control of the charge balance in the light emitting layer, quenching of the dopant, and light emission at the hole transport layer interface.

In the case of host materials for fluorescence and phosphorescence, recent studies have been made on increasing the efficiency and lifespan of organic electric devices using thermal activated delayed fluorescent (TADF), Exciplex, etc. A lot of research is in progress.

Although there are several methods for elucidating the energy transfer in the light emitting layer for thermal activated delayed fluorescent (TADF) and exciplex, it can be easily confirmed by PL lifetime (TRTP) measurement.

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

As such, there are various factors affecting the efficiency and lifespan depending on the method in which energy is transferred from the host material to the dopant material, and the energy transfer method is different depending on the material. This has not been done sufficiently. Therefore, the development of new materials is continuously required, and in particular, the development of the host material of the light emitting layer is urgently required.

The present invention has been proposed to solve the problems of the phosphorescent host material as described above, and the charge balance control in the light emitting layer, efficiency, and lifespan through the HOMO level control for the host material of the phosphorescent emission type organic electric device including the phosphorescent dopant. 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 is to reduce the energy barrier between the light emitting layer and the adjacent layer by containing a specific first host material and a specific second host material as a main component in order to control efficient hole injection into the light emitting layer of a phosphorescent light emitting organic electric device. This is to provide high efficiency and long life of organic electric devices by maximizing the charge balance in the light emitting layer.

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

Formula (1) Formula (2)

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

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

1 is an exemplary view 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 thereof will be omitted.

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

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

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

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond of 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

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

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group is replaced with a hetero atom.

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

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, 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. it is not

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 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 in the present invention 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 means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a reaction. 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 the radical substituted with an aryl group has the number of carbon atoms described herein.

Also, when prefixes are named consecutively, it is meant 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 and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" refers to an alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms each containing one or more heteroatoms, unless otherwise specified, No, it includes at least one of a single ring and a multiple ring, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" as used in the present invention, unless otherwise specified, contains one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heteroaliphatic ring aromatic rings. It may 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.

delete

Unless otherwise specified, as used herein, the term "aliphatic" refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" refers to 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 having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-mentioned heterocompounds include one or more heteroatoms, but are not limited thereto.

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

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" used in the present invention, "substitution" 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, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C ₂₀ heterocyclic group, but is not limited to these substituents.

In addition, unless there is an explicit explanation, the formula used in the present invention is the same as the definition of the substituent by the exponent definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 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.

In addition, unless otherwise explicitly stated, the terms "ortho", "meta", and "para" used in the present invention refer to the substitution positions of all substituents, and the ortho position refers to the substituents The position of represents a compound immediately adjacent, for example, in the case of benzene, it means 1 and 2 positions, and the meta position represents the next substitution position of the immediately neighboring substitution position. This means that the para position is the next substitution position of the meta position, and when benzene is used as an example, it means 1 or 4 positions. A more detailed description of the substitution position is as follows, and it can be seen that the ortho- and meta- (meta-) positions are substituted with a non-linear type, and the para- (para-) position is substituted with a linear type. have.

[ortho-position example]

[example of meta-location]

[example of meta-location]

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

Formula (1) Formula (2)

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

1) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an 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 An alkoxyl group; And C ₆ ~ C ₃₀ An aryloxy group; is selected from the group consisting of,

2) c and e are each independently an integer of 0 to 10, d is an integer of 0 to 2, R ³ , R ⁴ and R ⁵ are the same as or different from each other, and are each independently deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an 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 An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N(R _a )(R _b ); (Wherein L' is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorenylene group; C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ _{It is selected from the group consisting of a C 60 fused ring group of} an _aromatic ring _; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring, and O, N, S, Si and P C ₂ ~ C ₆₀ heterocyclic ring containing at least one heteroatom group; selected from the group consisting of), selected from the group consisting of, or, when c and e are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R ³ or a plurality of R ⁵ are bonded to each other to form a ring can do,

3) L ¹ , L ² , L ³ and L ⁴ are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; And C ₂ ~ C ₆₀ A heterocyclic group; selected from the group consisting of,

4) A and B are each independently a C ₆ ~ C ₂₀ aryl group or C ₂ ~ C ₂₀ heterocyclic group,

5) i and j are each independently 0 or 1,

provided that i + j is 1 or more, where i or j means a direct bond when i or j is 0,

6) X ¹ and X ² are independently of each other NR′, O, S, or CR′R″;

R' and R" are each independently hydrogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₃ ~ C ₆₀ Heterocyclic group; Or C ₁ ~ C ₅₀ Alkyl group;

R' and R" may combine with each other to form a spy ring,

Here, the aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkoxy group, and the aryloxy group are each deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; -L ^a -N(R ^a )(R ^b ); C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ An 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 C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; C ₂ -C ₂₀ A heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; 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 be combined with each other to form a ring, where the 'ring' means 3 to 60 carbon atoms Refers to a fused ring consisting of an aliphatic ring, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, including a saturated or unsaturated ring.}

In addition, compounds represented by the above formulas (1) and (2) are provided.

In addition, the present invention provides an organic electric device, characterized in that the first host compound represented by the formula (1) is represented by any one of the following formulas (3) to (5).

Chemical formula (3) Chemical formula (4) Chemical formula (5)

{In the above formulas (3) to (5),

1) L ¹ , L ³ , L ⁴ , Ar ² and Ar ³ is as defined above,

2) X ³ is O or S,

3) a is an integer from 0 to 4, b is an integer from 0 to 3, R ¹ and R ² are the same as or different from each other, and independently of each other, deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an 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 An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and ^{-L' -} N(R _a )(R _b ); They can combine with each other to form a ring.}

In addition, the present invention provides an organic electric device in which the compound represented by the formula (1) includes a compound represented by any one of the following formulas (6) to (14).

delete

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

Chemical formula (9) Chemical formula (10) Chemical formula (11)

Formula (12) Formula (13) Formula (14)

{In Formulas (6) to (14), L ¹ , L ³ , L ⁴ , Ar ² , Ar ³ , R ¹ , R ² , a and b are as defined in Formula (1) above.}

In another embodiment, the present invention provides an organic electric device in which the first host compound represented by the formula (1) includes a compound represented by any one of the following formulas (15) to (23).

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

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

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

{In Formulas (15) to (23), L ¹ , L ³ , L ⁴ , Ar ² , Ar ³ , R ¹ , R ² , a and b are as defined in Formula (1).}

As another example, the compound represented by the formula (1) provides an organic electric device including a compound represented by any one of the following formulas (24) to (26).

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

{In the above formulas (24) to (26),

1) L ¹ , L ³ , L ⁴ , Ar ² and Ar ³ are as defined above,

2) Ar ⁵ and Ar ⁶ are each independently a C ₆ ~ C ₆₀ aryl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an 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 An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L′-N(R _a )(R _b );

In the present invention, also in the formula (1), L ¹ , L ³ and L ⁴ It provides an organic electric device comprising a compound of any one of the following formulas (A-1) to (A-12).

{In the formulas (A-1) to (A-12),

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

2) R ⁶ , R ⁷ , and R ⁸ are the same as or different from each other and are each independently deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and 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 An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L' ^- N(R _a )(R _b ); ⁷ or adjacent R ⁶ and R ⁷ may be combined with each other to form an aromatic ring or a heteroaromatic ring,

2) Y is NR′, O, S or CR′R″, R′ and R″ are as defined above;

3) Z ¹ , Z ² and Z ³ are each independently CR′ or N, and at least one is N}

In one embodiment of the present invention, in Formula (1), at least one of L ¹ , L ³ and L ⁴ is necessarily a phenyl group and an organic electric device comprising a compound characterized in that it is substituted at the m (meta)-position to provide.

In another aspect, the present invention provides an organic electric device in which the second host compound represented by Formula (2) includes a compound represented by Formula (27) or Formula (28).

Formula (27) Formula (28)

{In Formulas (27) and (28), R ³ , R ⁴ , R ⁵ , Ar ⁴ , L ² , c, d, e, A, B, X ¹ and X ² are defined in Formula (2) above. It's like a bar.}

In addition, in one embodiment of the present invention, A and B of the formula (2) provides an organic electric device comprising a compound selected from the group consisting of the following formulas (B-1) to (B-7).

{In the formulas (B-1) to (B-7),

1) Z ⁴ to Z ⁵⁰ are each independently CR' or N,

2) R' is as defined above,

3) * indicates the condensed position.}

The present invention also provides an organic electric device in which the second host compound represented by the formula (2) includes a compound represented by any one of the following formulas (29) to (48).

Formula (29) Formula (30) Formula (31)

Formula (32) Formula (33) Formula (34)

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

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

Formula (41) Formula (42) Formula (43)

Formula (44) Formula (45) Formula (46)

Formula (47) Formula (48)

{In Formulas (29) to (48), Ar ⁴ , X ¹ , X ² , R ³ , R ⁴ , R ⁵ , c, d and e are as defined above.}

In one aspect of the present invention, the second host compound represented by the formula (2) provides an organic electric device including a compound represented by any one of the following formulas (49) to (56).

delete

Formula (49) Formula (50) Formula (51) Formula (52)

Formula (53) Formula (54) Formula (55) Formula (56)

{In Formulas (49) to (56), R ³ , R ⁴ , R ⁵ , Ar ⁴ , c, d, e, A, B, C and R′ are as defined above.}

In the present invention, the first host compound represented by the formula (1) includes the following compounds 1-1' to 1-82'.

Further, in the present invention, the second host compound represented by the formula (2) includes the following compounds 3-1 to 3-100.

Referring to FIG. 1 , the organic electric device 100 according to the present invention includes a first electrode 120 , a second electrode 180 , and a first electrode 120 and a second electrode formed on a substrate 110 . An organic material layer including the compound represented by Formula (1) is provided between (180). In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . In this case, the remaining layers except for the emission layer 150 may not be formed. It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like, and the electron transport layer 160 and the like may serve as a hole blocking layer.

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

On the other hand, even with the same core, the band gap, electrical properties, interface properties, etc. may vary depending on which position the substituent is bonded to, so the selection of the core and the combination of the sub-substituents coupled thereto are also very In particular, when the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, a long lifespan and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) 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 the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 and After forming the 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 electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160 .

In addition, one or more hole transport band layers are included between the first electrode and the light emitting layer, and the hole transport band layer includes a hole transport layer, a light emitting auxiliary layer, or both, and the hole transport band layer includes the above formula ( It is possible to provide an organic electric device including the compound represented by 1).

Accordingly, the present invention provides a light efficiency improving layer formed on at least one of one side opposite to the organic material layer among one side of the first electrode in the organic electric device or one side opposite to the organic material layer among one side of the second electrode. It provides an organic electric device further comprising.

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

As another specific example, the present invention provides an organic electric device in which the light emitting layer is a phosphorescent light emitting layer in the organic material layer.

The present invention also provides an organic electric device in which the compound represented by Chemical Formulas (1) and (2) is mixed in any one ratio of 1:9 to 9:1 in the emission layer of the organic material layer, and included in the emission layer.

In addition, the present invention is an organic electricity characterized in that in the light emitting layer of the organic material layer, the compound represented by Formula (1) and Formula (2) is mixed in any one ratio of 1:9 to 5:5 and used in the light emitting layer. provide the element. More preferably, the mixing ratio of the compound represented by the formula (1) and the formula (2) is 2:8 or 3:7, which is included in the light emitting layer.

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

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

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

In another aspect, the present invention provides an electronic device characterized in that the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for single color or white lighting. In this case, 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 system, a game machine, various TVs, and various computers.

Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (2) of the present invention and the preparation examples of the organic electric device of the present invention will be described in detail with reference to examples, but as the following examples of the present invention It is not limited.

[ Synthesis example One]

delete

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

<Scheme 1>

Sub 1 of example

Examples of Sub 1 of Scheme 1 are as follows, but are not limited thereto.

Synthesis example of Sub 2

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

delete

<Scheme 2>

[Example of Sub 2-1]

Aniline (15 g, 161.1 mmol), 1-bromonaphthalene (36.7 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.05 mmol), P(t-Bu) ₃ (3.26 g, 16.1 in a round-bottom flask) mmol), NaOt-Bu (51.08 g, 531.5 mmol), and toluene (1690 mL) were added, and then the reaction was carried out at 100°C. When the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 25.4 g of Sub 2-1. (Yield: 72%)

[Example of Sub 2-26]

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd in a round-bottom flask ₂ (dba) ₃ (4.06 g, 4.43 mmol), P(t-Bu) ₃ (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL) was added to Sub 2-1 above. 34.9 g of Sub 2-26 was obtained by the same method as in the experiment.

(Yield: 70%)

[Example of Sub 2-40]

In a round-bottom flask, naphthalen-1-amine (15 g, 104.8 mmol), 2-bromodibenzo[b,d]thiophene (30.3 g, 115.2 mmol), Pd ₂ (dba) ₃ (4.8 g, 5.24 mmol), P( t-Bu) ₃ (2.12 g, 10.48 mmol), NaOt-Bu (33.22 g, 345.7 mmol), and toluene (1100 mL) were tested in the same manner as in Sub 2-1 to obtain 24.9 g of Sub 2-40.

(Yield: 73%)

[Example of Sub 2-51]

In a round-bottom flask, 4-(dibenzo[b,d]furan-2-yl)aniline (15 g, 57.85 mmol), 2-bromodibenzo[b,d]furan (15.7 g, 63.63 mmol), Pd ₂ (dba) ₃ (2.65 g, 2.89 mmol), P(t-Bu) ₃ (1.17 g, 5.78 mmol), NaOt-Bu (18.35 g, 190.9 mmol), and toluene (607 mL) were prepared in the same manner as in Sub 2-1 above. By experiment, 17.2 g of Sub 2-51 was obtained. (Yield: 70%)

The following Sub 2-1 to Sub 2-52 were synthesized in the same manner as the synthesis method, and Sub 2 is not limited thereto.

compound FD-MS compound FD-MS Sub 2-1 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-2 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-3 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-4 m/z=169.09 (C ₁₂ H ₁₁ N=169.22) Sub 2-5 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-6 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-7 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-8 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-9 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-10 m/z=325.18 (C ₂₄ H ₂₃ N=325.45) Sub 2-11 m/z=397.18 (C ₃₀ H ₂₃ N=397.51) Sub 2-12 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-13 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-14 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-15 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-16 m/z=397.18 (C ₃₀ H ₂₃ N=397.51) Sub 2-17 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-18 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-19 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-20 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-21 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-22 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-23 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-24 m/z=473.21 (C ₃₆ H ₂₇ N=473.61) Sub 2-25 m/z=369.15 (C ₂₈ H ₁₉ N=369.46) Sub 2-26 m/z=561.25 (C ₄₃ H ₃₁ N=561.71) Sub 2-27 m/z=411.20 (C ₃₁ H ₂₅ N=411.54) Sub 2-28 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-29 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 2-30 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-31 m/z=475.19 (C ₃₅ H ₂₅ NO=475.58) Sub 2-32 m/z=575.22 (C ₄₃ H ₂₉ NO=575.70) Sub 2-33 m/z=533.21 (C ₄₁ H ₂₇ N=533.66) Sub 2-34 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-35 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-36 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-37 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-38 m/z=439.19 (C ₃₂ H ₂₅ NO=439.55) Sub 2-39 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-40 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-41 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-42 m/z=461.18 (C ₃₄ H ₂₃ NO=461.55) Sub 2-43 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-44 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-45 m/z=457.10 (C ₃₀ H ₁₉ NS ₂ =457.61) Sub 2-46 m/z=533.13 (C ₃₆ H ₂₃ NS ₂ =533.70) Sub 2-47 m/z=353.10 (C ₂₂ H ₁₅ N ₃ S=353.44) Sub 2-48 m/z=327.0 (C ₂₀ H ₁₃ N ₃ S=327.40) Sub 2-49 m/z=375.11 (C ₂₆ H ₁₇ NS=375.48) Sub 2-50 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-51 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.48) Sub 2-52 m/z=475.16 (C ₃₄ H ₂₁ NO ₂ =475.54)

Final Product Synthesis Example

Synthesis of 1-1'

di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 4-bromo-1,1'-biphenyl (8 g, 34.2 mmol), Pd ₂ (dba ) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol), and toluene (330 mL) were added and the reaction was carried out at 100°C. do. Upon completion of the reaction, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 11.3 g of Product 1-1'. (Yield: 77%)

Synthesis of 1-4'

bis(4-(naphthalen-1-yl)phenyl)amine (10 g, 23.7 mmol), 1-(4-bromophenyl)naphthalene (7.4 g, 26.1 mmol), Pd ₂ (dba) ₃ (1.09) in a round bottom flask g, 1.19 mmol), P(t-Bu) ₃ (0.5 g, 2.4 mmol), NaOt-Bu (7.52 g, 78.3 mmol), and toluene (250 mL) were tested in the same manner as in 1-1' above. 11.5 g of 1-4' was obtained. (Yield: 78%)

Synthesis of 1-10'

N-([1,1'-biphenyl]-4-yl)-[1,1':3',1''-terphenyl]-5'-amine (10 g, 25.2 mmol), 5 in a round bottom flask '-bromo-1,1':3',1''-terphenyl (8.56 g, 27.7 mmol), Pd ₂ (dba) ₃ (1.15 g, 1.26 mmol), P(t-Bu) ₃ (0.51 g, 2.52 mmol), NaOt-Bu (7.98 g, 83.02 mmol), and toluene (264 mL) were tested in the same manner as in 1-1' to obtain 11.8 g of Product 1-10'. (Yield: 75%)

Synthesis of 1-19'

N-([1,1'-biphenyl]-4-yl)naphthalen-1-amine (10 g, 33.6 mmol), 2-bromodibenzo[b,d]thiophene (9.8 g, 37.2 mmol), Pd ₂ (dba) ₃ (1.55 g, 1.7 mmol), P(t-Bu) ₃ (0.68 g, 3.38 mmol), NaOt-Bu (10.76 g, 112 mmol), toluene (355 mL) above 1-1 12.3 g of 'Product 1-19' was obtained by experimenting in the same manner as '. (Yield: 76%)

Synthesis of 1-20'

di([1,1'-biphenyl]-3-yl)amine (10 g, 31.1 mmol), 2-bromodibenzo[b,d]thiophene (9 g, 34.2 mmol), Pd ₂ (dba) in a round-bottom flask ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol), and toluene (327 mL) were prepared in the same manner as in 1-1' above. By experiment, 12.2 g of Product 1-20' was obtained. (Yield: 78%)

Synthesis of 1-23'

N-(naphthalen-1-yl)-9,9-diphenyl-9H-fluoren-2-amine (10 g, 21.8 mmol), 2-bromodibenzo[b,d]thiophene (6.3 g, 23.9 mmol) in a round-bottom flask ), Pd ₂ (dba) ₃ (1 g, 1.09 mmol), P(t-Bu) ₃ (0.44 g, 2.2 mmol), NaOt-Bu (6.9 g, 71.8 mmol), toluene (230 mL) above 1 10.2 g of Product 1-23' was obtained by experimenting in the same manner as -1'. (Yield: 73%)

Synthesis of 1-24'

N-([1,1'-biphenyl]-4-yl)-9,9'-spirobi[fluoren]-2-amine (10 g, 20.7 mmol), 2-bromodibenzo[b,d] in a round-bottom flask thiophene (6 g, 22.7 mmol), Pd ₂ (dba) ₃ (0.95 g, 1.03 mmol), P(t-Bu) ₃ (0.42 g, 2.07 mmol), NaOt-Bu (6.55 g, 68.2 mmol), toluene (220 mL) was tested in the same manner as in 1-1' to obtain 10.2 g of Product 1-24'. (Yield: 74%)

Synthesis of 1-29'

N-(naphthalen-1-yl)dibenzo[b,d]thiophen-2-amine (10 g, 30.7 mmol), 2-(4-bromophenyl)dibenzo[b,d]thiophene (11.5 g, 33.8 mmol), Pd ₂ (dba) ₃ (1.41 g, 1.54 mmol), P(t-Bu) ₃ (0.62 g, 3.07 mmol), NaOt-Bu (9.75 g, 101.4 mmol), toluene (325 mL) 12.9 g of Product 1-29' was obtained by experimenting in the same manner as in 1-1'. (Yield: 72%)

Synthesis of 1-30'

N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-3-amine (10 g, 31.1 mmol), 2-(3-bromophenyl)dibenzo[ b,d]thiophene (11.6 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.55 mmol), P(t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.9 g, 103) mmol) and toluene (330 mL) were tested in the same manner as in 1-1' to obtain 12.8 g of Product 1-30'. (Yield: 71%)

Synthesis of 1-36'

bis(dibenzo[b,d]thiophen-2-yl)amine (10 g, 26.2 mmol), 2-bromodibenzo[b,d]thiophene (7.59 g, 28.8 mmol), Pd ₂ (dba) ₃ in a round bottom flask (1.2 g, 1.31 mmol), P(t-Bu) ₃ (0.53 g, 2.62 mmol), NaOt-Bu (8.31 g, 86.5 mmol), and toluene (275 mL) were tested in the same manner as in 1-1' Thus, 11.4 g of Product 1-36' was obtained. (Yield: 77%)

Synthesis of 1-49'

di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 2-(3-bromophenyl)dibenzo[b,d]furan (11.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.9 g, 103 mmol), toluene (330 mL) above 1-1 13.3 g of 'Product 1-49' was obtained by the same method as '. (Yield: 76%)

Synthesis of 1-51'

N-(4-(naphthalen-1-yl)phenyl)naphthalen-2-amine (10 g, 28.9 mmol), 2-(7-bromo-9,9-dimethyl-9H-fluoren-2- yl)dibenzo[b,d]furan (14 g, 32 mmol), Pd ₂ (dba) ₃ (1.33 g, 1.45 mmol), P(t-Bu) ₃ (0.59 g, 2.9 mmol), NaOt-Bu ( 9.2 g, 95.5 mmol) and toluene (310 mL) were tested in the same manner as in 1-1' to obtain 14.5 g of Product 1-51'. (Yield: 71%)

Synthesis of 1-59'

N-([1,1'-biphenyl]-4-yl)benzo[4,5]thieno[3,2-d]pyrimidin-2-amine (10 g, 28.3 mmol), 4-( 4-bromophenyl)dibenzo[b,d]furan (10.1 g, 31.1 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.41 mmol), P(t-Bu) ₃ (0.57 g, 2.83 mmol), NaOt- Bu (8.98 g, 93.4 mmol) and toluene (300 mL) were tested in the same manner as in 1-1' to obtain 12.3 g of Product 1-59'. (Yield: 73%)

Synthesis of 1-71'

di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 2-(4-bromophenyl)-9,9'-spirobi[fluorene] (16.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol), toluene (330 mL) above 15.5 g of Product 1-71' was obtained in the same manner as 1-1'. (Yield: 70%)

Synthesis of 1-75'

N-(4-(9,9-diphenyl-9H-fluoren-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (10 g, 17.8 mmol), 3-bromo in a round bottom flask -9,9-diphenyl-9H-fluorene (7.78 g, 19.6 mmol), Pd ₂ (dba) ₃ (0.82 g, 0.89 mmol), P(t-Bu) ₃ (0.36 g, 1.78 mmol), NaOt-Bu (5.65 g, 58.75 mmol) and toluene (190 mL) were tested in the same manner as in 1-1' to obtain 11.3 g of Product 1-75'. (Yield: 72%)

compound FD-MS compound FD-MS 1-1' m/z=473.21 (C ₃₆ H ₂₇ N=473.61) 1-2' m/z=523.23 (C ₄₀ H ₂₉ N=523.66) 1-3' m/z=573.25 (C ₄₄ H ₃₁ N=573.72) 1-4' m/z=623.26 (C ₄₈ H ₃₃ N=623.78) 1-5' m/z=447.20 (C ₃₄ H ₂₅ N=447.57) 1-6' m/z=371.17 (C ₂₈ H ₂₁ N=371.47) 1-7' m/z=471.20 (C ₃₆ H ₂₅ N=471.59) 1-8' m/z=521.21 (C ₄₀ H ₂₇ N=521.65) 1-9' m/z=549.25 (C ₄₂ H ₃₁ N=549.70) 1-10' m/z=625.28 (C ₄₈ H ₃₅ N=625.80) 1-11' m/z=675.29 (C ₅₂ H ₃₇ N=675.86) 1-12' m/z=473.21 (C ₃₆ H ₂₇ N=473.61) 1-13' m/z=523.23 (C ₄₀ H ₂₉ N=523.66) 1-14' m/z=623.26 (C ₄₈ H ₃₃ N=623.78) 1-15' m/z=549.25 (C ₄₂ H ₃₁ N=549.70) 1-16' m/z=625.28 (C ₄₈ H ₃₅ N=625.80) 1-17' m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-18' m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-19' m/z=477.16 (C ₃₄ H ₂₃ NS=477.62) 1-20' m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-21' m/z=451.14 (C ₃₂ H ₂₁ NS=451.58) 1-22' m/z=593.22 (C ₄₃ H ₃₁ NS=593.78) 1-23' m/z=641.22 (C ₄₇ H ₃₁ NS=641.82) 1-24' m/z=665.22 (C ₄₉ H ₃₁ NS=665.84) 1-25' m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-26' m/z=655.23 (C ₄₈ H ₃₃ NS=655.85) 1-27' m/z=695.26 (C ₅₁ H ₃₇ NS=695.91) 1-28' m/z=593.18 (C ₄₂ H ₂₇ NOS=593.73) 1-29' m/z=583.14 (C ₄₀ H ₂₅ NS ₂ =583.76) 1-30' m/z=579.20 (C ₄₂ H ₂₉ NS=579.75) 1-31' m/z=685.19 (C ₄₈ H ₃₁ NS ₂ =685.90) 1-32' m/z=719.23 (C ₅₂ H ₃₃ NOS=719.89) 1-33' m/z=629.22 (C ₄₆ H ₃₁ NS=629.81) 1-34' m/z=629.22 (C ₄₆ H ₃₁ NS=629.81) 1-35' m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-36' m/z=563.08 (C ₃₆ H ₂₁ NS ₃ =563.75) 1-37' m/z=639.11 (C ₄₂ H ₂₅ NS ₃ =639.85) 1-38' m/z=715.15 (C ₄₈ H ₂₉ NS ₃ =715.95) 1-39' m/z=791.18 (C ₅₄ H ₃₃ NS ₃ =792.04) 1-40' m/z=607.16 (C ₄₂ H ₂₅ NO ₂ S=607.72) 1-41' m/z=633.21 (C ₄₅ H ₃₁ NOS=633.80) 1-42' m/z=733.24 (C ₅₃ H ₃₅ NOS=733.92) 1-43' m/z=883.29 (C ₆₅ H ₄₁ NOS=884.09) 1-44' m/z=585.13 (C ₃₈ H ₂₃ N ₃ S ₂ =585.74) 1-45' m/z=553.19 (C ₄₀ H ₂₇ NS=553.71) 1-46' m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-47' m/z=841.28 (C ₆₃ H ₃₉ NS=842.06) 1-48' m/z=563.22 (C ₄₂ H ₂₉ NO=563.69) 1-49' m/z=563.22 (C ₄₂ H ₂₉ NO=563.69) 1-50' m/z=613.24 (C ₄₆ H ₃₁ NO=613.76) 1-51' m/z=703.29 (C ₅₃ H ₃₇ NO=703.87) 1-52' m/z=587.22 (C ₄₄ H ₂₉ NO=587.71) 1-53' m/z=639.26 (C ₄₈ H ₃₃ NO=639.78) 1-54' m/z=639.26 (C ₄₈ H ₃₃ NO=639.78) 1-55' m/z=653.24 (C ₄₈ H ₃₁ NO ₂ =653.77) 1-56' m/z=603.26 (C ₄₅ H ₃₃ NO=603.75) 1-57' m/z=727.29 (C ₅₅ H ₃₇ NO=727.89) 1-58' m/z=725.27 (C ₅₅ H ₃₅ NO=725.87) 1-59' m/z=595.17 (C ₄₀ H ₂₅ N ₃ OS=595.71) 1-60' m/z=567.26 (C ₄₂ H ₃₃ NO=567.72) 1-61' m/z=611.22 (C ₄₆ H ₂₉ NO=611.73) 1-62' m/z=617.18 (C ₄₄ H ₂₇ NOS=617.76) 1-63' m/z=637.24 (C ₄₈ H ₃₁ NO=637.77) 1-64' m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.75) 1-65' m/z=767.25 (C ₅₆ H ₃₃ NO ₃ =767.87) 1-66' m/z=681.27 (C ₅₀ H ₃₅ NO ₂ =681.82) 1-67' m/z=658.22 (C ₄₅ H ₃₀ N ₄ S=658.82) 1-68' m/z=655.23 (C ₄₈ H ₃₃ NS=655.86) 1-69' m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.96) 1-70' m/z=784.27 (C ₅₅ H ₃₆ N ₄ S=784.98) 1-71' m/z=553.19 (C ₄₀ H ₂₇ NS=553.72) 1-72' m/z=553.19 (C ₄₀ H ₂₇ NS=553.72) 1-73' m/z=543.20 (C ₃₉ H ₂₉ NS=543.73) 1-74' m/z=671.21 (C ₄₈ H ₃₀ FNS=671.83) 1-75' m/z=641.25 (C ₄₆ H ₃₁ N ₃ O=641.77) 1-76' m/z=639.26 (C ₄₈ H ₃₃ NO=639.80) 1-77' m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.80) 1-78' m/z=614.24 (C ₄₅ H ₃₀ N ₂ O=614.75) 1-79' m/z=587.22 (C ₄₄ H ₂₉ NO=587.72) 1-80' m/z=613.24 (C ₄₆ H ₃₁ NO=613.76) 1-81' m/z=543.26 (C ₄₀ H ₃₃ NO=543.71) 1-82' m/z=667.25 (C ₄₉ H ₃₃ NO ₂ =667.81)

[ Synthesis example 2]

The compound represented by Formula (2) according to the present invention (final product 2) is prepared by reacting Sub 3 and Sub 4 as shown in Scheme 4 below.

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<Scheme 4>

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Sub 3 Synthesis Example

Sub 3 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto.

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<Scheme 5>

Sub 3(1) synthesis example

Sub 3-2-1 Synthesis Method

Sub 3-1-1 (40.8 g, 155 mmol), bis(pinacolato)diboron (43.4 g, 171 mmol), KOAc (46 g, 466 mmol), PdCl ₂ (dppf) (3.8 g, 4.7 mmol) in DMF (980 mL) was dissolved in a solvent, and then refluxed at 120 °C for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized using CH ₂ Cl ₂ and methanol solvent to obtain the desired Sub 3-2-1 (38.5 g, 80%).

Sub 3-4-1 Synthesis Method

Sub 3-2-1 (34.4 g, 111 mmol), Sub 3-3-1 (33.5 g, 133 mmol), K ₂ CO ₃ (46.03 g, 333 mmol), Pd(PPh ₃ ) ₄ ( 7.7 g, 6.66 mmol) was placed in a round bottom flask, dissolved in THF (490 mL) and water (245 mL), and then refluxed at 80° C. for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated using a silicagel column to obtain the desired Sub 3-4-1 (31.2 g, 79%).

Sub 3(1) Synthesis Method

Sub 3-4-1 (20g, 56.3 mmol) and triphenylphosphine (37 g, 141 mmol) obtained above were dissolved in o -dichlorobenzene (235 mL) and refluxed for 24 hours. When the reaction was completed, the solvent was removed by vacuum distillation, and the concentrated product was recrystallized by silicagel column to obtain the desired Sub 3(1) (14.7 g, 81%).

Sub 3(2) synthesis example

Sub 3-2-2 Synthesis Method

Sub 3-1-2 (40.8 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-2 (37.5 g, 78%).

Sub 3-4-2 Synthesis Method

Sub 3-2-2 (34.4 g, 111 mmol), Sub 3-3-1 (33.5 g, 133 mmol) was prepared by using the synthesis method of Sub 3-4-1 above to obtain the desired Sub 3-4-2 (30.4 g). , 77%) was obtained.

Sub 3(2) Synthesis Method

Sub 3-4-2 (20g, 56.3 mmol) was obtained by using the above synthesis method of Sub 3(1) to obtain the desired Sub 3(2) (14.4 g, 79%).

Sub 3(7) synthesis example

Sub 3-2-3 Synthesis Method

Sub 3-1-3 (57.7 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-3 (57.7 g, 78%).

Sub 3-4-3 Synthesis Method

Sub 3-2-3 (46.5 g, 111 mmol), Sub 3-3-2 (26.9 g, 133 mmol) was prepared by using the synthesis method of Sub 3-4-1 above to obtain the desired Sub 3-4-3 (37.3 g). , 81%) was obtained.

Sub 3(7) Synthesis Method

Sub 3-4-3. (23.3 g, 56.3 mmol) was used for the synthesis of Sub 3 (1) to obtain the desired Sub 3 (7) (17.9 g, 83%).

Sub 3(13) synthesis example

Sub 3-2-4 Synthesis Method

Sub 3-1-4 (53.8 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-4 (46.4 g, 76%).

Sub 3-4-4 Synthesis Method

Sub 3-2-4 (43.8 g, 111 mmol), Sub 3-3-2 (26.9 g, 133 mmol) was prepared by using the synthesis method of Sub 3-4-1 above for the desired Sub 3-4-4 (34.6 g). , 80%) was obtained.

Sub 3(13) Synthesis Method

Sub 3-4-4 (21.9 g, 56.3 mmol) was obtained by using the above synthesis method of Sub 3 (1) to obtain the desired Sub 3 (13) (16.3 g, 81%).

Sub 3(26) synthesis example

Sub 3-2-5 Synthesis Method

Sub 3-1-5 (50.1 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-5 (44.2 g, 76%).

Sub 3-4-5 Synthesis Method

Sub 3-2-5 (41.1 g, 111 mmol), Sub 3-3-3 (33.5 g, 133 mmol) was synthesized by using the above method for the synthesis of Sub 3-4-1 to the desired Sub 3-4-5 (37.4 g). , 81%) was obtained.

Sub 3(26) Synthesis Method

Sub 3-4-5 (23.4 g, 56.3 mmol) was obtained by using the above synthesis method of Sub 3 (1) to obtain the desired Sub 3 (26) (17.9 g, 83%).

Sub 3(39) synthesis example

Sub 3-2-6 Synthesis Method

Sub 3-1-6 (57.7 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-6 (51.3 g, 79%).

Sub 3-4-6 Synthesis Method

Sub 3-2-6 (46.5 g, 111 mmol), Sub 3-3-4 (33.5 g, 133 mmol) was prepared by using the synthesis method of Sub 3-4-1 above to obtain the desired Sub 3-4-6 (41.2 g). , 80%) was obtained.

Sub 3(39) Synthesis Method

Sub 3-4-6 (26.2 g, 56.3 mmol) was obtained by using the above synthesis method of Sub 3 (1) to obtain the desired Sub 3 (39) (19.7 g, 81%).

Sub 3(45) synthesis example

Sub 3-2-7 Synthesis Method

Sub 3-1-7 (46.1 g, 155 mmol) was synthesized by the above method of Sub 3-2-1 to obtain the desired Sub 3-2-7 (43.2 g, 81%).

Sub 3-4-7 Synthesis Method

Sub 3-2-7 (38.2 g, 111 mmol), Sub 3-3-3 (33.5 g, 133 mmol) was prepared by using the synthesis method of Sub 3-4-1 above to obtain the desired Sub 3-4-7 (36.7 g). , 85%) was obtained.

Sub 3(45) Synthesis Method

Sub 3-4-7 (21.9 g, 56.3 mmol) was obtained by using the above synthesis method of Sub 3 (1) to obtain the desired Sub 3 (45) (16.3 g, 81%).

Examples of Sub 3 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 3(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(2) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(3) m/z=307.10 (C ₂₂ H ₁₃ NO=307.34) Sub 3(4) m/z=307.10 (C ₂₂ H ₁₃ NO=307.34) Sub 3(5) m/z=333.15 (C ₂₅ H ₁₉ N=333.43) Sub 3(6) m/z=382.15 (C ₂₈ H ₁₈ N ₂ =382.46) Sub 3(7) m/z=382.15 (C ₂₈ H ₁₈ N ₂ =382.47) Sub 3(8) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(9) m/z=307.10 (C ₂₂ H ₁₃ NO=307.35) Sub 3(10) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(11) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(12) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(13) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(14) m/z=333.15 (C ₂₅ H ₁₉ N=333.43) Sub 3(15) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(16) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(17) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(18) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(19) m/z=407.13 (C ₃₀ H ₁₇ NO=407.47) Sub 3(20) m/z=433.18 (C ₃₃ H ₂₃ N=433.55) Sub 3(21) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(22) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(23) m/z=662.25 (C ₄₈ H ₃₀ N ₄ =662.80) Sub 3(24) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(25) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(26) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(27) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(28) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(29) m/z=307.10 (C ₂₂ H ₁₃ NO=307.35) Sub 3(30) m/z=455.17 (C ₃₅ H ₂₁ N=455.56) Sub 3(31) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(32) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(33) m/z=307.10 (C ₂₂ H ₁₃ NO=307.35) Sub 3(34) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(35) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =439.53) Sub 3(36) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(37) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(38) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(39) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(40) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(41) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(42) m/z=383.17 (C ₂₉ H ₂₁ N=383.49) Sub 3(43) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(44) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(45) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(46) m/z=505.18 (C ₃₉ H ₂₃ N=505.62) Sub 3(47) m/z=382.15 (C ₂₈ H ₁₈ N ₂ =382.47) Sub 3(48) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(49) m/z=307.10 (C ₂₂ H ₁₃ NO=307.35) Sub 3(50) m/z=333.15 (C ₂₅ H ₁₉ N=333.43) Sub 3(51) m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(52) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3(53) m/z=307.10 (C ₂₂ H ₁₃ NO=307.35) Sub 3(54) m/z=457.18 (C ₃₅ H ₂₃ N=457.58) Sub 3(55) m/z = 432.16 (C ₃₂ H ₂₀ N ₂ =432.53) Sub 3(56) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 3(57) m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) Sub 3(58) m/z=383.17 (C ₂₉ H ₂₁ N=383.49)

Sub 4 example

Examples of Sub 4 are as follows, but are not limited thereto.

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=205.97 (C ₁₀ H ₇ Br=207.07) Sub 4-3 m/z=205.97 (C ₁₀ H ₇ Br=207.07) Sub 4-4 m/z=231.99 (C ₁₂ H ₉ Br=233.10) Sub 4-5 m/z=309.02 (C ₁₇ H ₁₂ BrN=310.19) Sub 4-6 m/z=311.01 (C ₁₅ H ₁₀ BrN ₃ =312.16) Sub 4-7 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-8 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-9 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 4-10 m/z=387.04 (C ₂₁ H ₁₄ BrN ₃ =388.26) Sub 4-11 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.27) Sub 4-12 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.27) Sub 4-13 m/z=348.03 (C ₁₉ H ₁₃ BrN ₂ =349.22) Sub 4-14 m/z=271.99 (C ₁₃ H ₉ BrN ₂ =273.13) Sub 4-15 m/z=283.99 (C ₁₄ H ₉ BrN ₂ =285.14) Sub 4-16 m/z=374.01 (C ₂₀ H ₁₁ BrN ₂ O=375.22) Sub 4-17 m/z=400.06 (C ₂₃ H ₁₇ BrN ₂ =401.30) Sub 4-18 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.23) Sub 4-19 m/z=476.09 (C ₂₉ H ₂₁ BrN ₂ =477.39) Sub 4-20 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 4-21 m/z=289.03 (C ₁₄ H ₄ D ₅ BrN ₂ =290.2) Sub 4-22 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 4-23 m/z=375.00 (C ₁₉ H ₁₀ BrN ₃ O=376.2) Sub 4-24 m/z=401.05 (C ₂₂ H ₁₆ BrN ₃ =402.29) Sub 4-25 m/z=296.02 (C ₁₆ H ₉ ClN ₂ S=296.77) Sub 4-26 m/z=322.03 (C ₁₈ H ₁₁ ClN ₂ S=322.81) Sub 4-27 m/z=322.03 (C ₁₈ H ₁₁ ClN ₂ S=322.81) Sub 4-28 m/z=168.98 (C ₇ H ₄ ClNS=169.63) Sub 4-29 m/z=168.98 (C ₇ H ₄ ClNS=169.63)) Sub 4-30 m/z=169.97 (C ₆ H ₃ ClN ₂ S=170.62) Sub 4-31 m/z=246.00 (C ₁₂ H ₇ ClN ₂ S=246.72) Sub 4-32 m/z=322.03 (C ₁₈ H ₁₁ ClN ₂ S=322.81) Sub 4-33 m/z=322.03 (C ₁₈ H ₁₁ ClN ₂ S=322.81) Sub 4-34 m/z=168.98 (C ₇ H ₄ ClNS=169.63) Sub 4-35 m/z=168.98 (C ₇ H ₄ ClNS=169.63)) Sub 4-36 m/z=169.97 (C ₆ H ₃ ClN ₂ S=170.62) Sub 4-37 m/z=229.04 (C ₁₂ H ₈ ClN ₃ =229.67) Sub 4-38 m/z=279.06 (C ₁₆ H ₁₀ ClN ₃ =279.72) Sub 4-39 m/z=305.07 (C ₁₈ H ₁₂ ClN ₃ =305.76) Sub 4-40 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) Sub 4-41 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) Sub 4-42 m/z=229.04 (C ₁₂ H ₈ ClN ₃ =229.67) Sub 4-43 m/z=229.04 (C ₁₂ H ₈ ClN ₃ =229.67) Sub 4-44 m/z=279.06 (C ₁₆ H ₁₀ ClN ₃ =279.72) Sub 4-45 m/z=305.07 (C ₁₈ H ₁₂ ClN ₃ =305.76) Sub 4-46 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) Sub 4-47 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) Sub 4-48 m/z=229.04 (C ₁₂ H ₈ ClN ₃ =229.67) Sub 4-49 m/z=330.1 (C ₂₀ H ₁₁ ClN ₂ O=330.77) Sub 4-50 m/z=372.05 (C ₂₂ H ₁₃ ClN ₂ S=372.87) Sub 4-51 m/z=366.09 (C ₂₄ H ₁₅ ClN ₂ =366.85) Sub 4-52 m/z=340.08 (C ₂₂ H ₁₃ ClN ₂ =340.81) Sub 4-53 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) Sub 4-54 m/z=340.08 (C ₂₂ H ₁₃ ClN ₂ =340.81)

Final products 2 synthesis example

3-6 Synthesis Example

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Sub 3(1) (15.3 g, 47.3 mmol) was placed in a round-bottom flask and dissolved in toluene (500 mL), Sub 4-15 (14.8 g, 52.0 mmol), Pd ₂ (dba) ₃ (2.4 g, 2.6) mmol), P( t -Bu) ₃ (1.1 g, 5.2 mmol), and NaO t -Bu (15 g, 156.1 mmol) were added and stirred at 100°C. After completion of the reaction, extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 19.0 g (yield: 76%) of the product.

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3-1 Synthesis example

Sub 3(7) (18.1 g, 47.3 mmol), toluene (500 mL), Sub 4-1 (8.2 g, 52.0 mmol), Pd ₂ (dba) ₃ (2.0 g, 2.2 mmol), P( t -Bu ) ₃ (0.9 g, 4.4 mmol), NaO t -Bu (12.7 g, 132 mmol) was obtained by using the synthesis method of 3-6 above to obtain 16.7 g of a final product (yield: 77%).

3-7 Synthesis Example

Sub 3(1) (15.3 g, 47.3 mmol) and Sub 4-25 (15.4 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 19.6 g (yield: 71%) of the final product.

3-8 Synthesis Example

Sub 3(1) (15.3 g, 47.3 mmol) and Sub 4-53 (15.1 g, 52 mmol) were obtained by using the synthesis method of 3-6 above to obtain 19.9 g (yield: 73%) of the final product.

3-11 Synthesis Example

Sub 3 (13) (16.9 g, 47.3 mmol) and Sub 4-55 (16.1 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 19.4 g (yield: 70%) of the final product.

3-16 Synthesis Example

Sub 3 (17) (18.1 g, 47.2 mmol) and Sub 4-56 (16.7 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 21.0 g (yield: 71%) of the final product.

3-17 Synthesis example

Sub 3 (59) (20.5 g, 47.4 mmol) and Sub 4-57 (13.7 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 20.1 g (yield: 69%) of the final product.

3-47 Synthesis Example

Sub 3 (45) (16.9 g, 47.3 mmol) and Sub 4-58 (14.6 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 10.6 g (yield: 74%) of the final product.

3-52 Synthesis Example

Sub 3 (50) (15.8 g, 47.4 mmol) and Sub 4-12 (20.2 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 20.6 g (yield: 70%) of the final product.

3-70 Synthesis Example

Sub 3 (60) (17.7 g, 47.4 mmol) and Sub 4-59 (17.8 g, 52.0 mmol) were obtained by using the synthesis method of 3-6 above to obtain 22.8 g (yield: 73%) of the final product.

compound FD-MS compound FD-MS 3-1 m/z=458.18 (C ₃₄ H ₂₂ N ₂ =458.56) 3-2 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) 3-3 m/z=433.15 (C ₃₂ H ₁₉ NO=433.51) 3-4 m/z=535.23 (C ₄₁ H ₂₉ N=535.69) 3-5 m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) 3-6 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.65) 3-7 m/z=583.12 (C ₃₈ H ₂₁ N ₃ S ₂ =583.73) 3-8 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) 3-9 m/z=627.18 (C ₄₄ H ₂₅ N ₃ S=627.77) 3-10 m/z=475.14 (C ₃₄ H ₂₁ NS=475.61) 3-11 m/z=585.21 (C ₄₄ H ₂₇ NO=585.71) 3-12 m/z=509.21 (C ₃₉ H ₂₇ N=509.65) 3-13 m/z=509.19 (C ₃₇ H ₂₃ N ₃ =509.61) 3-14 m/z=451..11 (C ₃₀ H ₁₇ N ₃ S=451.55) 3-15 m/z=588.20 (C ₄₁ H ₂₄ N ₄ O=588.67) 3-16 m/z=624.26 (C ₄₇ H ₃₂ N ₂ =624.79) 3-17 m/z=614.18 (C ₄₄ H ₂₆ N ₂ S=614.77) 3-18 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) 3-19 m/z=573.17 (C ₄₂ H ₂₃ NO ₂ =573.65) 3-20 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.81) 3-21 m/z=624.26 (C ₄₇ H ₃₂ N ₂ =624.79) 3-22 m/z=603.18 (C ₄₂ H ₂₅ N ₃ S=603.74) 3-23 m/z=664.23 (C ₄₇ H ₂₈ N ₄ O=664.77) 3-24 m/z=737.28 (C ₅₅ H ₃₅ N ₃ =737.91) 3-25 m/z=738.28 (C ₅₄ H ₃₄ N ₄ =738.89) 3-26 m/z= 679.21 (C ₄₈ H ₂₉ N ₃ S=679.84) 3-27 m/z=625.22 (C ₄₅ H ₂₇ N ₃ O=625.73) 3-28 m/z=575.24 (C ₄₂ H ₂₉ N ₃ =575.72) 3-29 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) 3-30 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) 3-31 m/z=433.15 (C ₃₂ H ₁₉ NO=433.51) 3-32 m/z=531.20 (C ₄₁ H ₂₅ N=531.66) 3-33 m/z=608.23 (C ₄₆ H ₂₈ N ₂ =608.74) 3-34 m/z=475.14 (C ₃₄ H ₂₁ NS=475.61) 3-35 m/z=384.13 (C ₂₇ H ₁₆ N ₂ O=384.44) 3-36 m/z=614.25 (C ₄₄ H ₃₀ N ₄ =614.75) 3-37 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) 3-38 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) 3-39 m/z=433.15 (C ₃₂ H ₁₉ NO=433.51) 3-40 m/z=459.20 (C ₃₅ H ₂₅ N=459.59) 3-41 m/z=663.24 (C ₄₇ H ₂₉ N ₅ =663.78) 3-42 m/z=603.18 (C ₄₂ H ₂₅ N ₃ S=603.74) 3-43 m/z=587.20 (C ₄₂ H ₂₅ N ₃ O=587.68) 3-44 m/z=613.25 (C ₄₅ H ₃₁ N ₃ =613.76) 3-45 m/z=662.25 (C ₄₈ H ₃₀ N ₄ =662.80) 3-46 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) 3-47 m/z=601.18 (C ₄₂ H ₂₃ N ₃ O ₂ =601.67) 3-48 m/z=759.27 (C ₅₇ H ₃₃ N ₃ =759.91) 3-49 m/z=589.22 (C ₄₂ H ₂₆ N ₄ =586.70) 3-50 m/z=630.19 (C ₄₃ H ₂₆ N ₄ S=630.77) 3-51 m/z=613.22 (C ₄₄ H ₂₇ N ₃ O=613.72) 3-52 m/z=639.27 (C ₄₇ H ₃₃ N ₃ =639.80) 3-53 m/z=508.19 (C ₃₈ H ₂₄ N ₂ =508.62) 3-54 m/z=449.12 (C ₃₂ H ₁₉ NS=449.57) 3-55 m/z=433.15 (C ₃₂ H ₁₉ NO=433.51) 3-56 m/z=609.25 (C ₄₇ H ₃₁ N=609.77) 3-57 m/z=663.24 (C ₄₇ H ₂₉ N ₅ =663.78) 3-58 m/z=604.17 (C ₄₁ H ₂₄ N ₄ S=604.73) 3-59 m/z=587.20 (C ₄₂ H ₂₅ N ₃ O=587.68) 3-60 m/z613.25 (C ₄₅ H ₃₁ N ₃ =613.76) 3-61 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.65) 3-62 m/z=603.18 (C ₄₂ H ₂₅ N ₃ S=603.74) 3-63 m/z=511.17 (C ₃₆ H ₂₁ N ₃ O=511.58) 3-64 m/z=587.24 (C ₄₃ H ₂₉ N ₃ =587.73) 3-65 m/z=692.20 (C ₄₈ H ₂₈ N ₄ S=692.84) 3-66 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) 3-67 m/z=561.18 (C ₄₀ H ₂₃ N ₃ O=561.64) 3-68 m/z=653.19 (C ₄₆ H ₂₇ N ₃ S=653.80) 3-69 m/z=736.26 (C ₅₄ H ₃₂ N ₄ =736.88) 3-70 m/z=677.19 (C ₄₈ H ₂₇ N ₃ S=677.83) 3-71 m/z=687.23 (C ₅₀ H ₂₉ N ₃ O=687.80) 3-72 m/z=743.24 (C ₅₃ H ₃₃ N ₃ S=743.93) 3-73 m/z=703.21 (C ₅₀ H ₂₉ N ₃ S=703.86) 3-74 m/z=603.18 (C ₄₂ H ₂₅ N ₃ S=603.74) 3-75 m/z=735.18 (C ₅₀ H ₂₉ N ₃ S ₂ =735.92) 3-76 m/z=759.18 (C ₅₂ H ₂₉ N ₃ S ₂ =759.95) 3-77 m/z=475.14 (C ₃₄ H ₂₁ NS=475.61) 3-78 m/z=616.20 (C ₄₄ H ₂₈ N ₂ S=616.78) 3-79 m/z=710.16 (C ₄₇ H ₂₆ N ₄ S ₂ =710.87) 3-80 m/z=818.25 (C ₅₈ H ₃₄ N ₄ S=819.00) 3-81 m/z=603.18 (C ₄₂ H ₂₅ N ₃ S=603.74) 3-82 m/z=809.20 (C ₅₆ H ₃₁ N ₃ S ₂ =810.01) 3-83 m/z=659.15 (C ₄₄ H ₂₅ N ₃ S ₂ =659.83) 3-84 m/z=583.21 (C ₄₀ H ₂₉ N ₃ S=583.75) 3-85 m/z=844.27 (C ₆₀ H ₃₆ N ₄ S=845.04) 3-86 m/z=667.17 (C ₄₆ H ₂₅ N ₃ OS=667.79) 3-87 m/z=703.23 (C ₅₀ H ₂₉ N ₃ O ₂ =703.80) 3-88 m/z=629.21 (C ₄₄ H ₂₇ N ₃ O ₂ =629.72) 3-89 m/z=473.18 (C ₃₅ H ₂₃ NO=473.58) 3-90 m/z=600.22 (C ₄₄ H ₂₈ N ₂ O=600.72) 3-91 m/z=858.25 (C ₆₀ H ₃₄ N ₄ OS=859.02) 3-92 m/z=792.26 (C ₅₅ H ₃₂ N ₆ O=792.90) 3-93 m/z=514.24 (C ₃₈ H ₃₀ N ₂ =514.67) 3-94 m/z=701.28 (C ₅₂ H ₃₅ N ₃ =701.87) 3-95 m/z=700.26 (C ₅₁ H ₃₂ N ₄ =700.85) 3-96 m/z=764.29 (C ₅₆ H ₃₆ N ₄ =764.93) 3-97 m/z=700.29 (C ₅₃ H ₃₆ N ₂ =700.89 3-98 m/z=576.26 (C ₄₃ H ₃₂ N ₂ =576.74) 3-99 m/z=701.28 (C ₅₂ H ₃₅ N ₃ =701.87) 3-100 m/z=761.28 (C ₅₇ H ₃₅ N ₃ =761.93)

On the other hand, although exemplary synthesis examples of the present invention represented by the above formulas (1) and (2) have been described, these are all Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, and intramolecular acid-induced cyclization reaction (J. mater). Chem. 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization reaction (Org. Lett.2011, 13, 5504), Grignard reaction, cyclic dehydration reaction and PPh3-mediated reductive cyclization reaction (J. Org. Chem. 2005, 70, 5014.) and other substituents defined in formulas (1) and (2) in addition to the substituents specified in the specific synthesis examples (R ³ to R ⁵ , Ar ¹ to Ar ⁴ , L ¹ to L ² ) , X ^One To X ² ) It will be readily understood by those skilled in the art that the reaction proceeds even if it is combined.

For example, in Scheme 1, Sub 1 + Sub 2 -> Final Product 1 reaction, in Reaction Scheme 3 synthesizing Sub 2, in Reaction Scheme 4 Sub 3 + Sub 4 -> Final Product 2 reaction, all of them are for Buchwald-Hartwig cross coupling reaction. Sub 1-3 + Sub 1-4 -> Sub 1 reaction in Scheme 2, Sub 3-2 + Sub 3-3 -> Sub 3-4 reaction in Scheme 5 are all based on the Suzuki cross-coupling reaction, In Scheme 5, the Sub 3-4 -> Sub 3 reaction is based on the PPh3-mediated reductivecyclization reaction (J. Org. Chem. 2005, 70, 5014.). Even if a substituent not specifically specified is bonded, the above reactions will proceed.

Manufacturing evaluation of organic electric devices

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Example 1) Red Fabrication and testing of organic light emitting devices

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First, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl as a hole injection layer on the ITO layer (anode) formed on the glass substrate. )-N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum-deposited to form a thickness of 60 nm. Then, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was applied to a thickness of 60 nm. A hole transport layer was formed by vacuum deposition. A mixture of the inventive compound represented by Chemical Formulas (1) and (2) in a ratio of 3:7 was used as a host on the hole transport layer, and as a dopant, (piq) ₂ Ir(acac) [bis-(1-) phenylisoquinolyl)iridium(III)acetylacetonate] was doped at a weight of 95:5 to deposit a light emitting layer with a thickness of 30 nm on the hole transport layer. (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as BAlq) as a hole blocking layer was vacuum-deposited to a thickness of 10 nm, and an electron transport layer Tris(8-quinolinol)aluminum (hereinafter abbreviated as Alq3) was formed into a film to a thickness of 40 nm. Thereafter, LiF, which is an alkali metal halide, was deposited as an electron injection layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic electroluminescent device.

By applying a forward bias DC voltage to the organic electroluminescent devices of Examples and Comparative Examples prepared as described above, electroluminescence (EL) characteristics were measured with a PR-650 manufactured by photoresearch, and as a result of the measurement, 2500cd/m ² standard luminance T95 lifespan was measured using life measuring equipment manufactured by McScience. Table 6 below shows the device fabrication and evaluation results.

[Comparative Examples 1 to 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound represented by Formula 2 was used alone as a host.

[ comparative example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used alone as a host.

[ comparative example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used alone as a host.

[ comparative example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 was used alone as a host.

[ comparative example 7]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 4 was used alone as a host.

[ comparative example 8]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and Comparative Compound 2 were mixed and used as a host.

[ comparative example 9]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 and Comparative Compound 4 were mixed and used as a host.

[Comparative compound 1] [Comparative compound 2] [Comparative compound 3] [Comparative compound 4]

1st host 2nd host Voltage Current Density Brightness
(cd/m ² ) Efficiency Lifetime
T(95) Comparative Example (1) - compound (3-6) 6.6 19.1 2500.0 13.1 100.3 Comparative Example (2) - compound (3-61) 6.8 19.5 2500.0 12.8 98.8 Comparative Example (3) - compound (3-74) 6.9 20.2 2500.0 12.4 101.2 Comparative Example (4) - Comparative compound 1 7.3 22.5 2500.0 11.1 76.3 Comparative Example (5) - Comparative compound 2 7.2 21.7 2500.0 11.5 78.9 Comparative Example (6) - Comparative compound 3 7.1 21.0 2500.0 11.9 82.4 Comparative Example (7) - Comparative compound 4 7.4 22.3 2500.0 11.2 74.5 Comparative Example (8) Comparative compound 1 Comparative compound 2 6.5 14.8 2500.0 16.9 105.9 Comparative Example (9) Comparative compound 3 Comparative compound 4 6.4 13.7 2500.0 18.3 106.1 Example (1) Compound (1-4') compound (3-6) 5.6 8.7 2500.0 28.7 129.0 Example (2) Compound (1-10') compound (3-6) 5.9 8.8 2500.0 28.3 129.9 Example (3) Compound (1-16') compound (3-6) 5.5 8.5 2500.0 29.4 127.1 Example (4) Compound (1-21') compound (3-6) 5.6 7.8 2500.0 31.9 132.0 Example (5) compound (1-33') compound (3-6) 5.9 8.2 2500.0 30.6 131.6 Example (6) Compound (1-45') compound (3-6) 5.8 8.1 2500.0 30.7 132.0 Example (7) compound (1-48') compound (3-6) 5.6 7.8 2500.0 32.2 132.4 Example (8) Compound (1-50') compound (3-6) 5.8 7.7 2500.0 32.3 133.0 Example (9) compound (1-55') compound (3-6) 5.9 7.6 2500.0 32.9 132.9 Example (10) compound (1-56') compound (3-6) 5.7 7.7 2500.0 32.7 132.5 Example (11) Compound (1-4') compound (3-7) 5.8 10.9 2500.0 23.0 120.8 Example (12) Compound (1-10') compound (3-7) 6.0 10.8 2500.0 23.2 120.4 Example (13) Compound (1-16') compound (3-7) 5.6 11.0 2500.0 22.7 120.5 Example (14) Compound (1-21') compound (3-7) 5.6 10.1 2500.0 24.6 121.9 Example (15) compound (1-33') compound (3-7) 5.6 10.2 2500.0 24.4 122.8 Example (16) Compound (1-45') compound (3-7) 5.6 9.7 2500.0 25.6 121.4 Example (17) compound (1-48') compound (3-7) 5.7 9.3 2500.0 26.8 124.5 Example (18) Compound (1-50') compound (3-7) 5.8 9.6 2500.0 26.1 124.2 Example (19) compound (1-55') compound (3-7) 5.7 9.5 2500.0 26.5 124.8 Example (20) compound (1-56') compound (3-7) 5.7 9.6 2500.0 26.0 123.1 Example (21) Compound (1-4') compound (3-8) 5.8 11.1 2500.0 22.6 120.4 Example (22) Compound (1-10') compound (3-8) 6.0 11.3 2500.0 22.1 120.6 Example (23) Compound (1-16') compound (3-8) 5.9 11.1 2500.0 22.4 120.1 Example (24) Compound (1-21') compound (3-8) 5.6 10.2 2500.0 24.4 122.3 Example (25) compound (1-33') compound (3-8) 5.6 9.8 2500.0 25.5 122.4 Example (26) Compound (1-45') compound (3-8) 5.7 10.2 2500.0 24.6 121.9 Example (27) compound (1-48') compound (3-8) 5.9 9.5 2500.0 26.4 123.4 Example (28) Compound (1-50') compound (3-8) 5.7 9.5 2500.0 26.3 123.5 Example (29) compound (1-55') compound (3-8) 5.8 9.3 2500.0 26.8 124.3 Example (30) compound (1-56') compound (3-8) 5.9 9.5 2500.0 26.3 124.8 Example (31) Compound (1-4') compound (3-9) 5.5 10.8 2500.0 23.2 120.6 Example (32) Compound (1-10') compound (3-9) 5.9 11.2 2500.0 22.4 120.3 Example (33) Compound (1-16') compound (3-9) 5.8 11.1 2500.0 22.6 120.1 Example (34) Compound (1-21') compound (3-9) 5.8 10.0 2500.0 25.0 121.2 Example (35) compound (1-33') compound (3-9) 5.7 10.3 2500.0 24.4 122.8 Example (36) Compound (1-45') compound (3-9) 5.6 9.6 2500.0 25.9 122.9 Example (37) compound (1-48') compound (3-9) 5.6 9.3 2500.0 26.8 125.0 Example (38) Compound (1-50') compound (3-9) 5.9 9.6 2500.0 26.2 124.1 Example (39) compound (1-55') compound (3-9) 5.7 9.4 2500.0 26.5 124.0 Example (40) compound (1-56') compound (3-9) 5.7 9.4 2500.0 26.7 124.9 Example (41) Compound (1-4') compound (3-15) 5.6 10.6 2500.0 23.7 120.0 Example (42) Compound (1-10') compound (3-15) 5.9 11.0 2500.0 22.7 120.6 Example (43) Compound (1-16') compound (3-15) 5.8 10.7 2500.0 23.5 120.9 Example (44) Compound (1-21') compound (3-15) 5.8 10.3 2500.0 24.2 122.4 Example (45) compound (1-33') compound (3-15) 5.6 10.2 2500.0 24.6 121.7 Example (46) Compound (1-45') compound (3-15) 5.8 10.1 2500.0 24.8 122.3 Example (47) compound (1-48') compound (3-15) 5.7 9.6 2500.0 26.2 123.5 Example (48) Compound (1-50') compound (3-15) 5.8 9.5 2500.0 26.3 123.5 Example (49) compound (1-55') compound (3-15) 5.9 9.3 2500.0 27.0 123.2 Example (50) compound (1-56') compound (3-15) 5.7 9.5 2500.0 26.2 123.7 Example (51) Compound (1-4') compound (3-37) 5.6 10.5 2500.0 23.8 120.5 Example (52) Compound (1-10') compound (3-37) 5.7 11.2 2500.0 22.3 120.6 Example (53) Compound (1-16') compound (3-37) 5.6 10.6 2500.0 23.5 121.0 Example (54) Compound (1-21') compound (3-37) 6.0 10.0 2500.0 25.1 122.5 Example (55) compound (1-33') compound (3-37) 5.5 10.3 2500.0 24.2 122.4 Example (56) Compound (1-45') compound (3-37) 5.7 9.7 2500.0 25.7 122.3 Example (57) compound (1-48') compound (3-37) 6.0 9.5 2500.0 26.2 124.7 Example (58) Compound (1-50') compound (3-37) 5.9 9.3 2500.0 26.9 123.6 Example (59) compound (1-55') compound (3-37) 5.9 9.4 2500.0 26.7 124.2 Example (60) compound (1-56') compound (3-37) 5.6 9.4 2500.0 26.6 124.0 Example (61) Compound (1-4') compound (3-46) 5.5 11.3 2500.0 22.2 120.9 Example (62) Compound (1-10') compound (3-46) 5.6 10.8 2500.0 23.2 120.2 Example (63) Compound (1-16') compound (3-46) 5.8 11.0 2500.0 22.7 120.7 Example (64) Compound (1-21') compound (3-46) 5.6 10.1 2500.0 24.8 122.5 Example (65) compound (1-33') compound (3-46) 5.9 9.8 2500.0 25.5 121.1 Example (66) Compound (1-45') compound (3-46) 5.5 10.2 2500.0 24.5 121.8 Example (67) compound (1-48') compound (3-46) 5.8 9.3 2500.0 26.8 124.3 Example (68) Compound (1-50') compound (3-46) 5.7 9.3 2500.0 26.9 124.6 Example (69) compound (1-55') compound (3-46) 5.6 9.4 2500.0 26.6 124.8 Example (70) compound (1-56') compound (3-46) 5.9 9.3 2500.0 26.8 124.8 Example (71) Compound (1-4') compound (3-50) 5.9 11.2 2500.0 22.3 120.7 Example (72) Compound (1-10') compound (3-50) 5.9 10.8 2500.0 23.1 120.1 Example (73) Compound (1-16') compound (3-50) 5.8 11.2 2500.0 22.2 120.7 Example (74) Compound (1-21') compound (3-50) 5.8 10.3 2500.0 24.2 122.5 Example (75) compound (1-33') compound (3-50) 5.5 9.8 2500.0 25.5 122.1 Example (76) Compound (1-45') compound (3-50) 5.5 10.2 2500.0 24.5 121.6 Example (77) compound (1-48') compound (3-50) 5.7 9.5 2500.0 26.2 123.4 Example (78) Compound (1-50') compound (3-50) 6.0 9.4 2500.0 26.6 123.2 Example (79) compound (1-55') compound (3-50) 5.8 9.6 2500.0 26.1 124.5 Example (80) compound (1-56') compound (3-50) 5.6 9.3 2500.0 26.9 124.0 Example (81) Compound (1-4') compound (3-61) 5.9 9.4 2500.0 26.5 120.1 Example (82) Compound (1-10') compound (3-61) 5.5 9.5 2500.0 26.4 120.1 Example (83) Compound (1-16') compound (3-61) 6.0 9.3 2500.0 26.8 120.8 Example (84) Compound (1-21') compound (3-61) 6.0 9.2 2500.0 27.1 121.6 Example (85) compound (1-33') compound (3-61) 5.5 9.2 2500.0 27.1 122.7 Example (86) Compound (1-45') compound (3-61) 5.6 9.0 2500.0 27.8 121.9 Example (87) compound (1-48') compound (3-61) 5.8 8.6 2500.0 29.0 123.0 Example (88) Compound (1-50') compound (3-61) 5.8 8.6 2500.0 29.2 123.7 Example (89) compound (1-55') compound (3-61) 5.6 8.8 2500.0 28.4 124.6 Example (90) compound (1-56') compound (3-61) 5.9 8.8 2500.0 28.5 124.0 Example (91) Compound (1-4') compound (3-74) 5.9 10.9 2500.0 23.0 120.3 Example (92) Compound (1-10') compound (3-74) 5.6 10.6 2500.0 23.5 120.1 Example (93) Compound (1-16') compound (3-74) 5.8 11.1 2500.0 22.5 120.2 Example (94) Compound (1-21') compound (3-74) 5.5 10.3 2500.0 24.3 121.3 Example (95) compound (1-33') compound (3-74) 5.7 10.3 2500.0 24.2 122.6 Example (96) Compound (1-45') compound (3-74) 6.0 10.0 2500.0 25.1 121.8 Example (97) compound (1-48') compound (3-74) 6.0 9.5 2500.0 26.5 124.0 Example (98) Compound (1-50') compound (3-74) 5.6 9.4 2500.0 26.5 123.3 Example (99) compound (1-55') compound (3-74) 5.6 9.3 2500.0 26.8 124.0 Example 100 compound (1-56') compound (3-74) 5.9 9.6 2500.0 26.1 124.3
As can be seen from the results of Table 6, when the material for an organic electroluminescent device of the present invention represented by Chemical Formula (1) and Chemical Formula (2) is mixed and used as a phosphorescent host (Examples 1 to 100), a single material is used It was confirmed that the driving voltage, efficiency, and lifespan were significantly improved compared to the devices (Comparative Examples 1 to 7). More specifically, in Comparative Examples 1 to 7, wherein the compound of the present invention represented by Formula (2) and Comparative Compounds 1 to 4 alone were used as phosphorescent hosts, the compounds of the present invention (3-6, 3-61 , 3-74) using Comparative Examples 1 to 3 showed higher efficiency and higher lifespan than Comparative Examples 4 to 7 using the comparative compound.

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In addition, Comparative Examples 8 and 9, which were used as phosphorescent hosts by mixing Comparative Compound 1 and Comparative Compound 2 or Comparative Compound 3 and Comparative Compound 4, showed higher efficiency than Comparative Examples 1 to 7 using the single material. could confirm that Comparing Comparative Example 8 and Comparative Example 9, compared to Comparative Example 8 in which a 5-cyclic heterocyclic compound having the same nitrogen atom was mixed, a heteropolycyclic cyclic compound having different heteroatoms (N, S) among the 5-cyclic cyclic compounds It was confirmed that Comparative Example 9 using the containing mixture exhibited higher efficiency.

And it was confirmed that Examples 1 to 100 using a mixture of the compounds of Formula (1) and Formula (2), which are compounds of the present invention, as hosts, exhibit significantly higher efficiency and lifespan than in Comparative Examples 1 to 9. and it was confirmed that a low driving voltage was exhibited.

Based on the experimental results, the present inventors judged that the material obtained by mixing the material of Formula (1) and the material of Formula (2) has novel properties other than the properties of each material, and PL lifetime was measured using the substance, the substance of formula (2), and the inventive mixture, respectively. As a result, when the compounds of the present invention, Chemical Formulas (1) and (2) were mixed, it was confirmed that a new PL wavelength was formed, unlike the case of a single compound. And it was confirmed that the decrease and extinction time of each of the substances of formula (2) increased from about 60 times to about 360 times as much as possible. This means that when the compound of the present invention is mixed and used, not only electrons and holes are moved through the energy level of each material, but also electrons and holes are moved or energy by exciplex having a new energy level formed by mixing. It is judged that the efficiency and lifespan of the delivery are increased. As a result, when the mixture of the present invention is used, it can be said that the mixed thin film is an important example showing exciplex energy transfer and light emission processes.

In addition, the reason why the combination of the present invention is superior to Comparative Examples 8 to 9 using a phosphorescent host in which the comparative compound is mixed is that the polycyclic compound represented by the formula (2) has characteristics such as stability to electrons as well as holes and high T1. When the compound represented by Formula (1) with strong hole properties is mixed, electron blocking ability is improved due to high T1 and high LUMO energy value, and more holes move quickly and easily in the light emitting layer. As a result, the charge balance in the light emitting layer between holes and electrons is increased, so that light is emitted well inside the light emitting layer, not at the interface of the hole transport layer. . In addition, it was confirmed that among the compounds represented by Formula (1), the compound substituted with dibenzofuran showed the best results in terms of driving voltage, efficiency, and lifespan. could check That is, in conclusion, it is considered that the combination of Chemical Formulas (1) and (2) is electrochemically synergistic to improve the overall performance of the device.

Example 2) by mixing ratio Red Fabrication and testing of organic light emitting devices

1st host 2nd host mixing ratio
(1st host: 2nd host) Voltage Current Density Brightness
(cd/m2) Efficiency Lifetime
T(95) Example 101 Compound (1-33') compound (3-61) 2:8 5.5 9.1 2500.0 27.4 123.0 embodiment (102) compound (1-33') compound (3-61) 3:7 5.5 9.2 2500.0 27.1 122.7 Example (103) compound (1-33') compound (3-61) 4:6 5.7 9.7 2500.0 25.9 120.1 embodiment (104) Compound (1-33') compound (3-61) 5:5 6.0 10.8 2500.0 23.1 119.4 Example (105) Compound (1-50') compound (3-6) 2:8 5.7 7.4 2500.0 33.6 133.6 Example (106) Compound (1-50') compound (3-6) 3:7 5.8 7.7 2500.0 32.3 133.0 Example (107) Compound (1-50') compound (3-6) 4:6 6.1 8.1 2500.0 30.7 130.5 embodiment (108) Compound (1-50') compound (3-6) 5:5 6.3 8.8 2500.0 28.4 128.4

As shown in Table 7 above, the mixture of the compounds of the present invention was measured by manufacturing a device in each ratio (2:8, 3:7, 4:6, 5:5). To explain the results in detail, in the results of the mixture of compound 1-33' and compound 3-61, the results of driving voltage, efficiency, and lifespan were similarly excellent for 2:8 and 3:7, but 4:6, 5:5 and As the ratio of the first host increased, it was confirmed that the results of driving voltage, efficiency, and lifespan gradually decreased, which was the same in the result of the mixture of Compound 1-50' and Compound 3-6. This can be explained 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 properties such as 2:8 and 3:7 is mixed.

The above description is merely illustrative of the present invention, and various modifications will be possible without departing from the essential characteristics of the present invention by those of ordinary skill in the art to which the present invention pertains. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, 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 by 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 device 110: substrate
120: first electrode (anode) 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)

Claims (19)

In the organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer, a first host compound represented by 1) and a second host compound represented by the following formula (2), wherein the compound represented by formula (1) and formula (2) is in a weight ratio of 1:9 to 9:1 An organic electric device, characterized in that it is mixed in any one ratio.
Formula (1) Formula (2)

{In the above formulas (1) and (2),
1) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₃₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; A fused ring group of C ₃ ~ C ₃₀ aliphatic ring and C ₆ ~ C ₃₀ aromatic ring; And C ₁ ~ C ₃₀ Alkyl group; is selected from the group consisting of,
However, Ar ¹ , Ar ² and Ar ³ Any one of O, N, S, Si and P except for the case of a C ₁₆ ~ C ₃₀ heterocyclic group containing at least one heteroatom,
2) c and e are each independently an integer of 0 to 10, d is an integer of 0 to 2, R ³ , R ⁴ and R ⁵ are the same as or different from each other, and are each independently deuterium; halogen; C ₆ ~ C ₃₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; A fused ring group of C ₃ ~ C ₃₀ aliphatic ring and C ₆ ~ C ₃₀ aromatic ring; C ₁ ~ C ₃₀ Alkyl group; and a C ₂ ~ C ₂₀ alkenyl group; or selected from the group consisting of, or when c and e are 2 or more, a plurality of the same or different from each other and a plurality of R ³ or a plurality of R ⁵ are bonded to each other to form a ring can be formed,
3) L ¹ , L ² , L ³ and L ⁴ are a single bond independently of each other; C ₆ ~ C ₃₀ Arylene group; fluorenylene group; A fused ring group of C ₃ ~ C ₃₀ aliphatic ring and C ₆ ~ C ₃₀ aromatic ring; And C ₂ ~ C ₃₀ A heterocyclic group; selected from the group consisting of,
4) A and B are each independently a C ₆ ~ C ₂₀ aryl group or C ₂ ~ C ₂₀ heterocyclic group,
5) i and j are each independently 0 or 1,
provided that i + j is 1 or more, where i or j means a direct bond when i or j is 0,
6) X ¹ and X ² are independently of each other NR′, O, S, or CR′R″;
R' and R" are each independently hydrogen; C ₆ ~ C ₃₀ Aryl group; Fluorenyl group; C ₃ ~ C ₃₀ Heterocyclic group; Or C ₁ ~ C ₃₀ Alkyl group;
R' and R" may combine with each other to form a spy ring,

Here, the aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fused ring group, the alkyl group, and the alkenyl group are each deuterium; halogen; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₂₀ An alkoxyl group; C ₆ -C ₂₀ Aryl group; a C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; And C ₂ -C ₂₀ A heterocyclic group; may be further substituted with one or more substituents selected from the group consisting of.}
The organic electric device according to claim 1, wherein the first host compound represented by the formula (1) is represented by any one of the following formulas (3) to (5).
Chemical formula (3) Chemical formula (4) Chemical formula (5)

{In the above formulas (3) to (5),
1) L ¹ , L ³ , L ⁴ , Ar ² and Ar ³ are as defined in claim 1 above,
2) X ³ is O or S,
3) a is an integer from 0 to 4, b is an integer from 0 to 3, R ¹ and R ² are the same as or different from each other, and independently of each other, deuterium; halogen; C ₆ ~ C ₂₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₂₀ A heterocyclic group; And C ₁ ~ C ₂₀ Alkyl group; selected from the group consisting of.}
The organic electric device according to claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas (6) to (14).
Formula (6) Formula (7) Formula (8)

Chemical formula (9) Chemical formula (10) Chemical formula (11)

Formula (12) Formula (13) Formula (14)

{In Formulas (6) to (14), L ¹ , L ³ , L ⁴ , Ar ² , Ar ³ , R ¹ , R ² , a and b are as defined in claim 1 above.}
The method according to claim 1, wherein Ar ¹ , Ar ² and Ar ³ of Formula (1) are all C ₆ -C ₂₄ aryl groups and L ¹ , L ³ , L ⁴ An organic electric device, characterized in that the compound is a single bond or all C ₆ ~ C ₂₄ aryl group
The organic electric device according to claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas (24) to (26).
Formula (24) Formula (25) Formula (26)

{In the above formulas (24) to (26),
1) L ¹ , L ³ , L ⁴ , Ar ² and Ar ³ are as defined in claim 1 above,
2) Ar ⁵ and Ar ⁶ are each independently a C ₆ ~ C ₃₀ aryl group; Or O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; is.}
According to claim 1, wherein in the formula (1) L ¹ , L ³ And L ⁴ An organic electric device, characterized in that the compound in any one of the following formulas (A-1) to (A-12)

{In the formulas (A-1) to (A-12),
1) a', c', d' and e' are each independently an integer of 0-4; b' is an integer from 0 to 6; f' and g' are independent of each other An integer from 0 to 3, h' is an integer from 0 or 1,
2) R ⁶ , R ⁷ and R ⁸ are the same as or different from each other, and independently of each other, deuterium; halogen; C ₆ ~ C ₂₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₂₀ A heterocyclic group; And C ₁ ~ C ₂₀ Alkyl group; selected from the group consisting of, or when f ' and g' are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R ⁶ , or a plurality of R ⁷ , or adjacent R ⁶ and R ⁷ may combine with each other to form an aromatic ring or a heteroaromatic ring,
2) Y is NR', O, S or CR'R", R' and R" are as defined in claim 1 above,
3) Z ¹ , Z ² and Z ³ are each independently CR′ or N, and at least one is N}
According to claim 1, wherein in the formula (1) L ¹ , At least one of L ³ and L ⁴ is an organic electric device, characterized in that the compound is substituted with a meta (meta) position
The organic electric device according to claim 1, wherein the second host compound represented by the formula (2) is represented by the following formula (27) or formula (28).
Formula (27) Formula (28)

{In Formulas (27) and (28), R ³ , R ⁴ , R ⁵ , Ar ⁴ , L ² , c, d, e, A, B, X ¹ and X ² are as defined in claim 1 above. .}
The organic electric device according to claim 1, wherein A and B of the formula (2) are selected from the group consisting of the following formulas (B-1) to (B-7).

{In the formulas B-1 to B-7,
1) Z ⁴ to Z ⁵⁰ are each independently CR' or N,
2) R' is as defined in claim 1 above,
3) * indicates the condensed position.}
The organic electric device according to claim 1, wherein the second host compound represented by the formula (2) is represented by any one of the following formulas (29) to (48).
Formula (29) Formula (30) Formula (31)

Formula (32) Formula (33) Formula (34)

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

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

Formula (41) Formula (42) Formula (43)

Formula (44) Formula (45) Formula (46)

Formula (47) Formula (48)

{In Formulas (29) to (48), Ar ⁴ , X ¹ , X ² , R ³ , R ⁴ , R ⁵ , c, d and e are as defined in claim 1 above.}
The organic electric device according to claim 1, wherein the second host compound represented by the formula (2) is represented by any one of the following formulas (49) to (56).
Formula (49) Formula (50) Formula (51) Formula (52)

Formula (53) Formula (54) Formula (55) Formula (56)

{In the above formulas (49) to (56),
R ³ , R ⁴ , R ⁵ , Ar ⁴ , c, d, e, A, B and R' are as defined in claim 1 above.}
The organic electric device according to claim 1, wherein the first host compound represented by the formula (1) is any one of the following compounds.

The organic electric device according to claim 1, wherein the second host compound represented by the formula (2) is any one of the following compounds 3-1 to 3-100.

The method according to claim 1, comprising at least one hole transport band layer 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 comprising a compound represented by the formula (1).
delete The organic electric device according to claim 1, wherein the compound represented by Chemical Formula (1) and Chemical Formula (2) is mixed in a weight ratio of 1:9 to 5:5 and used in the light emitting layer.
The organic electric device according to claim 1, wherein the compound represented by Chemical Formula (1) and Chemical Formula (2) is mixed in a weight ratio of 2:8 or 3:7 and used in the light emitting layer.
A display device comprising the organic electric device of claim 1; and a control unit for driving the display device;
19. The method of claim 18,
The organic electric device is an electronic device, characterized in that at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a single color or white lighting device.

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