KR102403291B1 - Compound for organic electronic element and organic electronic element comprising the same - Google Patents

Abstract

The present invention relates to a compound for an organic electronic device and an organic electronic device comprising the same, and more specifically, to a compound for an organic electronic device which copolymerizes a monomer having a specific structure with various aromatic arylene derivative compounds or vinyl monomers to implement a low crosslinking temperature of the compound for an organic electronic device, which is a copolymer so that the compound is thermally decomposed or the optical properties are changed to improve the lifespan of the organic electronic device and easily form a multi-layered thin film.

Description

A compound for an organic electronic device and an organic electronic device comprising the same

The present invention relates to a compound for an organic electronic device and an organic electronic device including the same, and specifically, by copolymerizing a monomer having a specific structure and various aromatic arylene derivative compounds or vinyl-based monomers, the copolymer is a compound for an organic electronic device A compound for an organic electronic device that can improve the lifespan of an organic electronic device and easily form a multilayer thin film by thermally decomposing the compound or changing optical properties by implementing a low crosslinking temperature of the compound and an organic electronic device including the same will be.

The organic electronic device refers to a device that performs an electrical operation using at least one organic material. The organic electronic device reduces power consumption and has the advantage of being able to be manufactured at a relatively low cost compared to the conventional inorganic electronic device.

Organic electronic devices generally include organic light emitting devices, organic solar cells, organic memory devices, organic sensors, organic thin film transistors and organic supercapacitors. The organic electronic device has a multi-layer structure, and when the electronic device is formed in a large size, the vacuum deposition method has high process cost and technical limitations.

On the other hand, the solution process method using a polymer can easily form a thin film by a method such as spin coating or inkjet printing, and it does not require a separate vacuum technology, so equipment costs can be reduced. In this case, there is an advantage in that the device can be easily manufactured without loss of material. Therefore, from a commercial point of view in the long term, it is expected that a device using a high molecular material rather than a low molecular material will have greater competitiveness when applied to a large display.

However, when the device is manufactured by a solution process method using a polymer, there is a problem of dissolving the already formed lower layer. The present invention relates to a compound for an organic electronic device and an organic electronic device comprising the same, and by including a specific structure, solvent resistance can be imparted so as not to damage the lower film during lamination through crosslinking at low temperature.

The technical problem to be achieved by the present invention is by using a copolymer including a specific structure as a compound for an organic electronic device so that when a device is manufactured by a solution process using a polymer, the lower layer can be cross-linked at a low temperature. An object of the present invention is to provide a compound for an organic electronic device having improved solvent resistance to prevent damage to the lower layer through low-temperature crosslinking in the lamination process, and an organic electronic device including the same.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention provides a compound for an organic electronic device represented by the following structural formula (1).

[Structural Formula 1]

이며, Ar¹은 각각 치환된 C6 내지 C60 아릴렌기, 또는 치환된 C2 내지 C60 헤테로아릴렌기이고, Ar² 및 Ar³는 서로 같거나 다르고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C60 아릴렌기, 또는 치환 또는 비치환된 C2 내지 C60 헤테로아릴렌기이며, 상기 “*”은 연결지점이다.In Structural Formula 1, x, y and z are the number of repeating units, the ratio of x, y and z is x: y + z = 0.01 to 0.99: 0.99 to 0.01, n is 1 to 4, and R ¹ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted or an unsubstituted C1 to C30 heteroarylene group, a substituted or unsubstituted C1 to C30 alkoxyylene group, a substituted or unsubstituted C3 to C30 cycloalkoxyylene group, a substituted or unsubstituted C1 to C30 heterocycloalkoxyylene group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group, wherein R ² is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 Alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted C1 to C30 heterocycloalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, or substituted or unsubstituted C1 to C30 hetero an aryloxy group, and X ¹ is an oxygen atom or

and Ar ¹ are each a substituted C6 to C60 arylene group, or a substituted C2 to C60 heteroarylene group, Ar ² and Ar ³ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 arylene group, Or a substituted or unsubstituted C2 to C60 heteroarylene group, wherein “*” is a connection point.

An exemplary embodiment of the present invention provides a compound for an organic electronic device represented by the following structural formula (2).

[Structural Formula 2]

,

및

이고, 상기 R³은 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 시클로알킬렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C3 내지 C30 시클로알콕실렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕실렌기, 치환 또는 비치환된 C6 내지 C30 아릴옥실렌기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥실렌기이며, 상기 R⁴ 내지 R⁷ 는 서로 같거나 다르고, 각각 독립적으로 수소원자, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C3 내지 C30 시클로알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥시기이고, 상기 X² 내지 X⁴는 서로 같거나 다르고, 각각 독립적으로 산소원자 또는

이며, 상기 Q¹ 및 Q²는 서로 같거나 다르고, 각각 독립적으로

,

,

및

이고, 상기 R⁸ 내지 R¹²는 서로 같거나 다르고, 각각 독립적으로 수소원자, 불소원자, 치환 또는 비치환된 C1 내지 C30 플루오로알킬기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고, 상기 R⁸ 내지 R¹² 중에서 적어도 어느 하나는 불소원자, 또는 치환 또는 비치환된 C1 내지 C30 플루오로알킬기이며, 상기 R¹³ 및 R¹⁴은 서로 같거나 다르고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 시클로알킬렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C3 내지 C30 시클로알콕실렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕실렌기, 치환 또는 비치환된 C6 내지 C30 아릴옥실렌기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥실렌기이며, 상기 X⁵ 및 X⁶는 서로 같거나 다르고, 각각 독립적으로 산소원자 또는

이고, Ar⁴ 내지 Ar⁶는 치환 또는 비치환된 C6 내지 C60 아릴렌기, 또는 치환 또는 비치환된 C2 내지 C60 헤테로아릴렌기이며, 상기 “*”은 연결지점이다.In Structural Formula 2, k, l and m are the number of repeating units, the ratio of k, l and m is k: l + m = 0.01 to 0.99: 0.99 to 0.01, n is 1 to 4, P ¹ silver

,

and

and R ³ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 Arylene group, substituted or unsubstituted C1 to C30 heteroarylene group, substituted or unsubstituted C1 to C30 alkoxyylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocyclo an alkoxyylene group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group, wherein R ⁴ to R ⁷ are the same as or different from each other, and each independently a hydrogen atom , substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted C1 to C30 heterocycloalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, or a substituted or unsubstituted C1 to C30 heteroaryloxy group, wherein X ² to X ⁴ are the same as or different from each other, and each independently an oxygen atom or

and Q ¹ and Q ² are the same as or different from each other, and each independently

,

,

and

and R ⁸ to R ¹² are the same as or different from each other, and each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, wherein among R ⁸ to R ¹² At least one is a fluorine atom or a substituted or unsubstituted C1 to C30 fluoroalkyl group, wherein R ¹³ and R ¹⁴ are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted A substituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C30 heteroarylene group, a substituted or unsubstituted C1 to C30 alkoxyylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocycloalkoxyylene group, substituted or unsubstituted C6 to C30 aryloxyylene group, or substituted or an unsubstituted C1 to C30 heteroaryloxyylene group, wherein X ⁵ and X ⁶ are the same as or different from each other, and each independently an oxygen atom or

and Ar ⁴ to Ar ⁶ are a substituted or unsubstituted C6 to C60 arylene group, or a substituted or unsubstituted C2 to C60 heteroarylene group, wherein “*” is a connection point.

An exemplary embodiment of the present invention provides an organic electronic device including an organic layer, wherein the organic layer includes the compound for an organic electronic device.

The compound for an organic electronic device according to an exemplary embodiment of the present invention can realize a low crosslinking temperature by copolymerizing a monomer having a specific structure and various aromatic arylene compounds or vinyl-based monomers, and can easily form a multilayer thin film .

The organic electronic device according to an exemplary embodiment of the present invention includes a compound for an organic electronic device having a low crosslinking temperature in the organic layer, thereby preventing thermal decomposition caused by high-temperature crosslinking, minimizing changes in optical properties, and improving device lifespan. can

Effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and accompanying drawings.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, "A and/or B" means "A and B, or A or B."

Throughout this specification, the term "monomer unit" may refer to a form in which a monomer is reacted in a polymer, and specifically, the monomer undergoes a polymerization reaction to form a backbone of the polymer, for example, a main chain or a side chain. It can mean the shape forming the .

Throughout this specification, the term "repeat unit" may refer to a form in which a monomer is reacted and repeated in a polymer, and specifically, the monomer undergoes a polymerization reaction to repeat in the backbone of the polymer, for example, the main chain or side chain. It may mean a form that forms a structured structure.

Throughout this specification, “compound X” may mean a compound including a compound having a structure of Formula X or a compound having a structure of Formula X.

Throughout this specification, terms including an ordinal number such as first, second, etc. may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

Throughout this specification, when a component is referred to as being “formed” or “stacked” on another component, it may be formed or laminated directly attached to the front surface or one surface on the surface of the other component. However, it may mean that there may be more other components in the middle.

Throughout this specification, "substituted" means that at least one hydrogen atom is deuterium, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C1 to C30 halogenated alkyl group, C6 to C30 aryl group, C1 to C30 Heteroaryl group, C1 to C30 alkoxy group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryloxy group, silyloxy group (-OSiH ₃ ), -OsiR`H <sub>2</sub> (R` is C1 to C30 Alkyl group or C6 to C30 aryl group), -OsiR`R``H (R` and R`` are each independently a C1 to C30 alkyl group or C6 to C30 aryl group), -OsiR`R``R```, (R`, R``, and R``` are each independently a C1 to C30 alkyl group or C6 to C30 aryl group), C1 to C30 acyl group, C2 to C30 acyloxy group, C2 to C30 heteroaryloxy group, C1 to C30 sulfonyl group, C1 to C30 alkylthiol group, C6 to C30 arylthiol group, C1 to C30 heterocyclothiol group, C1 to C30 phosphate amide group, silyl group (SiR`R``R```) (R `, R``, and R``` are each independently a hydrogen atom, a C1 to C30 alkyl group or a C6 to C30 aryl group), an amine group (-NR`R``) (herein, R` and R`` are each independently a hydrogen atom, a substituent selected from the group consisting of a C1 to C30 alkyl group, and a C6 to C30 aryl group), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group, and a hydroxyl group selected from the group consisting of It means substituted with a substituent.

Throughout this specification, two adjacent substituents among the above substituents may be fused to form a saturated or unsaturated ring.

Throughout this specification, the carbon number range of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group", etc. does not consider the portion in which the substituent is substituted. It refers to the total number of carbon atoms constituting the alkyl part or the aryl part when viewed as unsubstituted. Specifically, the phenyl group substituted with a butyl group at the para position means that it corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

Throughout the present specification, the carbon number range of the fused aryl group in the "substituted or unsubstituted C6 to C30 fused aryl group" etc. is fused when viewed as unsubstituted without considering the portion in which the substituent is substituted. It means the total number of carbons constituting the newly formed aryl moiety.

Throughout this specification, unless otherwise defined, "hetero" means that one functional group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. .

Throughout the present specification, "their bond" means that, unless otherwise defined, two or more substituents are bonded to a linking group, or two or more substituents are condensed and bonded.

Throughout this specification, "hydrogen" means singlet, deuterium, or tritium, unless otherwise defined.

Throughout this specification, the term "alkyl group" refers to an aliphatic hydrocarbon group unless otherwise defined.

Throughout this specification, the alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

Throughout this specification, the alkyl group may be an "unsaturated alkyl group" containing at least one double bond or triple bond.

Throughout this specification, "alkenylene group" refers to a functional group in which at least two carbon atoms are formed of at least one carbon-carbon double bond, and "alkynylene group" refers to at least two carbon atoms having at least one refers to a functional group consisting of a carbon-carbon triple bond. Alkyl groups, whether saturated or unsaturated, can be branched, straight-chain or cyclic.

Throughout this specification, the alkyl group may be a C1 to C30 alkyl group. More specifically, it may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group. Specifically, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, that is, the alkyl chain is composed of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. indicates selected from the group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, and the like.

Throughout this specification, "amine group" includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be expressed as -NR`R``, where R` and R`` is each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group.

Throughout this specification, "cycloalkyl group" includes monocyclic or fused-ring polycyclic (ie, rings having adjacent pairs of carbon atoms) functional groups.

Throughout the present specification, "heterocycloalkyl group" means that the cycloalkyl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heterocycloalkyl group is a fused ring, at least one ring of the fused ring may include 1 to 4 hetero atoms.

Throughout the present specification, the term "aromatic group" refers to a functional group in which all elements of a ring-shaped functional group have p-orbitals, and these p-orbitals form a conjugate. Specific examples include an aryl group and a heteroaryl group.

Throughout this specification, "aryl group" includes monocyclic or fused ring polycyclic (ie, rings having adjacent pairs of carbon atoms) functional groups.

Throughout this specification, "heteroaryl group" means that it contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P in the aryl group, and the remainder is carbon. When the heteroaryl group is a fused ring, at least one ring among the fused rings may include 1 to 4 hetero atoms.

Throughout this specification, the number of atoms in the ring in the aryl group and the heteroaryl group is the sum of the number of carbon atoms and the number of non-carbon atoms.

Throughout this specification, when used in combination with "alkylaryl group" or "arylalkyl group", each of the terms alkyl and aryl have the meaning and content indicated above. Specifically, the term "arylalkyl group" refers to an aryl substituted alkyl radical such as benzyl and is included in the alkyl group. Furthermore, the term "alkylaryl group" refers to an alkyl-substituted aryl radical and is included in the aryl group.

Hereinafter, the present invention will be described in more detail.

An exemplary embodiment of the present invention provides a compound for an organic electronic device represented by the following structural formula (1).

[Structural Formula 1]

이며, Ar¹은 각각 치환된 C6 내지 C60 아릴렌기, 또는 치환된 C2 내지 C60 헤테로아릴렌기이고, Ar² 및 Ar³는 서로 같거나 다르고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C60 아릴렌기, 또는 치환 또는 비치환된 C2 내지 C60 헤테로아릴렌기이며, 상기 “*”은 연결지점이다.In Structural Formula 1, x, y and z are the number of repeating units, the ratio of x, y and z is x: y + z = 0.01 to 0.99: 0.99 to 0.01, n is 1 to 4, and R ¹ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted or an unsubstituted C1 to C30 heteroarylene group, a substituted or unsubstituted C1 to C30 alkoxyylene group, a substituted or unsubstituted C3 to C30 cycloalkoxyylene group, a substituted or unsubstituted C1 to C30 heterocycloalkoxyylene group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group, wherein R ² is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 Alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted C1 to C30 heterocycloalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, or substituted or unsubstituted C1 to C30 hetero an aryloxy group, and X ¹ is an oxygen atom or

and Ar ¹ are each a substituted C6 to C60 arylene group, or a substituted C2 to C60 heteroarylene group, Ar ² and Ar ³ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 arylene group, Or a substituted or unsubstituted C2 to C60 heteroarylene group, wherein “*” is a connection point.

The compound for an organic electronic device according to an exemplary embodiment of the present invention can realize a low crosslinking temperature by copolymerizing a monomer having a specific structure and various aromatic arylene compounds or vinyl-based monomers, and can easily form a multilayer thin film .

According to an exemplary embodiment of the present invention, Ar ¹ to Ar ³ may be as follows.

,

,

,

,

,

,

,

,

또는

이고, 상기 "

"은 치환지점이고, 상기 X⁷ 는 산소원자, 황원자 또는

이고, 상기 Ar² 및 Ar³은 서로 같거나 다르고, 각각 독립적으로

,

,

,

,

,

,

,

,

,

,

,

,

,

,

또는

이고, 상기 X⁸ 및 X⁹는 서로 같거나 다르고, 각각 독립적으로 산소원자, 황원자 또는

이며, 상기 R¹⁵ 내지 R⁵⁹은 서로 같거나 다르고, 각각 독립적으로 수소원자, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기일 수 있다. 상술한 것으로부터 Ar¹ 내지 Ar³를 선택함으로써, 상기 유기전자소자용 화합물의 가교온도를 낮게 구현할 수 있다.The Ar ¹ is

,

,

,

,

,

,

,

,

or

, and said "

"is a substitution point, wherein X ⁷ is an oxygen atom, a sulfur atom, or

and Ar ² and Ar ³ are the same as or different from each other, and each independently

,

,

,

,

,

,

,

,

,

,

,

,

,

,

or

and X ⁸ and X ⁹ are the same as or different from each other, and each independently an oxygen atom, a sulfur atom or

and R ¹⁵ to R ⁵⁹ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or It may be an unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C1 to C30 heteroaryl group. By selecting Ar ¹ to Ar ³ from the above, the crosslinking temperature of the compound for an organic electronic device may be reduced.

는 하기 화학식 1 내지 화학식 18 중 선택된 하나인 것일 수 있다.According to an exemplary embodiment of the present invention, in Structural Formula 1

may be one selected from the following Chemical Formulas 1 to 18.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

을 선택함으로써, 다층박막을 용이하게 형성할 수 있으며, 상기 가교된 박막층의 용매저항성을 향상시킬 수 있다.In the above-mentioned Formulas 1 to 18, included in the Structural Formula 1

By selecting , a multilayer thin film can be easily formed, and the solvent resistance of the crosslinked thin film layer can be improved.

According to an exemplary embodiment of the present invention, Ar ² and Ar ³ in Structural Formula 1 may each independently be selected from the following Chemical Formulas 27 to 32.

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

By selecting Ar ² and Ar ³ from the aforementioned Chemical Formulas 27 to 32, a low crosslinking temperature of the compound for an organic electronic device can be realized.

According to an exemplary embodiment of the present invention, Structural Formula 1 may be one selected from the following Chemical Formulas 37 to 39.

[Formula 37]

[Formula 38]

[Formula 39]

By selecting Structural Formula 1 from the aforementioned Chemical Formulas 37 to 39, a low crosslinking temperature can be realized, and a multilayer thin film can be easily formed.

An exemplary embodiment of the present invention provides a compound for an organic electronic device represented by the following structural formula (2).

[Structural Formula 2]

,

및

이고, 상기 R³은 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 시클로알킬렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C3 내지 C30 시클로알콕실렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕실렌기, 치환 또는 비치환된 C6 내지 C30 아릴옥실렌기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥실렌기이며, 상기 R⁴ 내지 R⁷ 는 서로 같거나 다르고, 각각 독립적으로 수소원자, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C3 내지 C30 시클로알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥시기이고, 상기 X² 내지 X⁴는 서로 같거나 다르고, 각각 독립적으로 산소원자 또는

이며, 상기 Q¹ 및 Q²는 서로 같거나 다르고, 각각 독립적으로

,

,

및

이고, 상기 R⁸ 내지 R¹²는 서로 같거나 다르고, 각각 독립적으로 수소원자, 불소원자, 치환 또는 비치환된 C1 내지 C30 플루오로알킬기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고, 상기 R⁸ 내지 R¹² 중에서 적어도 어느 하나는 불소원자, 또는 치환 또는 비치환된 C1 내지 C30 플루오로알킬기이며, 상기 R¹³ 및 R¹⁴은 서로 같거나 다르고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 시클로알킬렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C1 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C3 내지 C30 시클로알콕실렌기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알콕실렌기, 치환 또는 비치환된 C6 내지 C30 아릴옥실렌기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴옥실렌기이며, 상기 X⁵ 및 X⁶는 서로 같거나 다르고, 각각 독립적으로 산소원자 또는

이고, Ar⁴ 내지 Ar⁶는 치환 또는 비치환된 C6 내지 C60 아릴렌기, 또는 치환 또는 비치환된 C2 내지 C60 헤테로아릴렌기이며, 상기 “*”은 연결지점이다.In Structural Formula 2, k, l and m are the number of repeating units, the ratio of k, l and m is k: l + m = 0.01 to 0.99: 0.99 to 0.01, n is 1 to 4, P ¹ silver

,

and

and R ³ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 Arylene group, substituted or unsubstituted C1 to C30 heteroarylene group, substituted or unsubstituted C1 to C30 alkoxyylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocyclo an alkoxyylene group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group, wherein R ⁴ to R ⁷ are the same as or different from each other, and each independently a hydrogen atom , substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted C1 to C30 heterocycloalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, or a substituted or unsubstituted C1 to C30 heteroaryloxy group, wherein X ² to X ⁴ are the same as or different from each other, and each independently an oxygen atom or

and Q ¹ and Q ² are the same as or different from each other, and each independently

,

,

and

and R ⁸ to R ¹² are the same as or different from each other, and each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, wherein among R ⁸ to R ¹² At least one is a fluorine atom or a substituted or unsubstituted C1 to C30 fluoroalkyl group, wherein R ¹³ and R ¹⁴ are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted A substituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C30 heteroarylene group, a substituted or unsubstituted C1 to C30 alkoxyylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocycloalkoxyylene group, substituted or unsubstituted C6 to C30 aryloxyylene group, or substituted or an unsubstituted C1 to C30 heteroaryloxyylene group, wherein X ⁵ and X ⁶ are the same as or different from each other, and each independently an oxygen atom or

and Ar ⁴ to Ar ⁶ are a substituted or unsubstituted C6 to C60 arylene group, or a substituted or unsubstituted C2 to C60 heteroarylene group, wherein “*” is a connection point.

The compound for an organic electronic device according to an exemplary embodiment of the present invention can realize a low crosslinking temperature by copolymerizing a monomer having a specific structure and various aromatic arylene compounds or vinyl-based monomers, and can easily form a multilayer thin film .

,

,

,

,

,

,

,

또는

인 것일 수 있다. 본 발명의 일 실시상태에 따른 유기전자소자용 화합물은 특정한 구조를 포함하는 단량체와 다양한 방향족 아릴렌 화합물 또는 바이닐계 단량체를 공중합시킴으로써 가교 온도를 낮게 구현할 수 있으며, 다층 박막을 용이하게 형성시킬 수 있다.According to an exemplary embodiment of the present invention, Ar ⁴ to Ar ⁶ may be as follows. The Ar ⁴ To Ar ⁶ Are the same as or different from each other, and each independently

,

,

,

,

,

,

,

or

may be The compound for an organic electronic device according to an exemplary embodiment of the present invention can realize a low crosslinking temperature by copolymerizing a monomer having a specific structure and various aromatic arylene compounds or vinyl-based monomers, and can easily form a multilayer thin film .

는 하기 화학식 19 내지 화학식 26 중 선택된 하나인 것일 수 있다.According to an exemplary embodiment of the present invention, in Structural Formula 2

may be one selected from the following Chemical Formulas 19 to 26.

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

를 선택하으로써, 가교 온도를 낮게 구현할 수 있으며, 다층 박막을 용이하게 형성시킬 수 있다.From the above-mentioned Formulas 19 to 26, in Structural Formula 2

By selecting , a low crosslinking temperature can be realized, and a multilayer thin film can be easily formed.

According to an exemplary embodiment of the present invention, in Structural Formula 2, Q ¹ and Q ² may each independently be selected from the following Chemical Formulas 33 to 36.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

By selecting each of Q ¹ and Q ² in Structural Formula 2 from Chemical Formulas 33 to 36 described above, a low crosslinking temperature can be realized, and a multilayer thin film can be easily formed.

According to an exemplary embodiment of the present invention, Structural Formula 2 may be one selected from the following Chemical Formulas 40 to 42.

[Formula 40]

[Formula 41]

[Formula 42]

By selecting Structural Formula 2 from the aforementioned Chemical Formulas 40 to 42, a low crosslinking temperature can be realized, and a multilayer thin film can be easily formed.

An exemplary embodiment of the present invention provides an organic electronic device including an organic layer, wherein the organic layer includes the compound for an organic electronic device.

The organic electronic device according to an exemplary embodiment of the present invention includes a compound for an organic electronic device having a low crosslinking temperature in the organic layer, thereby preventing thermal decomposition caused by high-temperature crosslinking, minimizing changes in optical properties, and improving device lifespan. can

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.

<Examples and Comparative Examples>

The compound for an organic electronic device represented by Structural Formula 1 or 2 of the present invention may be prepared by polymerization through Yamamoto coupling or Suzuki coupling radical polymerization, but the scope of the present invention is limited thereto. it is not going to be

<Example 1: Synthesis of compound for organic electronic device represented by Chemical Formula 37>

[Scheme 1]

Preparation Example 1-1. Synthesis of Intermediate 37-1

[Scheme 1-1]

Benzocyclobutene (20.0 g, 192.0 mmol), N-bromosuccinimide (41.0 g, 230.4 mmol), and benzoyl peroxide (0.47 g, 2.0 mmol) were dissolved in chlorobenzene (240 mL) at 85 ° C. 24 stirred for hours. After completion of the reaction, after cooling, the resultant product is obtained by distillation after filtering with n-hexane. (yield rate: 67%)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.35 - 7.27 (m, 2H), 7.17 (dd, J = 9.6, 4.0 Hz, 1H), 7.12 (d, J = 6.6 Hz, 1H), 5.46 ( dd, J = 4.8, 2.1 Hz, 1H), 3.90 (dd, J = 14.7, 4.6 Hz, 1H), 3.45 (dd, 1H).

Preparation 1-2. Synthesis of Intermediate 37-2

[Scheme 1-2]

Intermediate 37-1 (23.0 g, 125.6 mmol), pentan-1-ol (11.08 g, 125.6 mmol), and sodium hydride (3.62 g, 150.8 mmol) were dissolved in dimethylformamide (600 mL) at 60 ° C. 24 stirred for hours. After completion of the reaction, after cooling, extraction with ethyl acetate is used to obtain a product through column chromatography. (yield rate: 62%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.24 - 7.20 (m, J = 10.0 Hz, 2H), 7.20 - 7.17 (m, 1H), 4.96 (t, 1H), 3.49 (t) , 2H), 3.15 - 3.10 (m, 1H), 2.90 - 2.85 (m, 1H), 1.61 - 1.54 (m, 2H), 1.44 - 1.36 (m, 2H), 1.36 - 1.28 (m, 2H), 0.99 (t, 3H).

Preparation Example 1-3. Synthesis of intermediate 37-3

[Scheme 1-3]

Intermediate 37-2 (14.0 g, 73.6 mmol) and distilled water (75 ml) were added while stirring at 0 °C, and bromine (11.76 g, 73.6 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is used to obtain a product through column chromatography. (yield rate: 71%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.16 - 3.11 (m) , 1H), 2.90 - 2.86 (m, 1H), 1.60 - 1.54 (m, 2H), 1.42 - 1.36 (m, 2H), 1.35 - 1.29 (m, 2H), 0.99 (t, 3H).

Preparation Example 1-4. Synthesis of intermediate 37-4

[Scheme 1-4]

Intermediate 37-3 (14.0 g, 52.0 mmol) was dissolved in tetrahydrofuran (190 ml), tert -butyllithium (61.32 ml, 2M) was added while stirring at -78 °C, and stirred at -78 °C for 30 minutes. Then, 1,3-dibromopropane (42.32 g, 209.6 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 74%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.45 (t, 2H) ), 3.15 - 3.11 (m, 1H), 2.90 - 2.86 (m, 1H), 2.53 (t, 2H), 2.21 - 2.16 (m, 2H), 1.61 - 1.54 (m, 2H), 1.43 - 1.37 (m) , 2H), 1.36 - 1.30 (m, 2H), 0.99 (t, 3H).

Preparation Example 1-5. Synthesis of intermediate 37-5

[Scheme 1-5]

2,7-dibromo-9-fluorene (20.0 g, 61.7 mmol) and potassium tert-butoxide (1.94 g, 61.7 mmol) were dissolved in tetrahydrofuran (180 mL) and stirred at room temperature for 1 hour. did. After completion of the reaction, distilled water is added to precipitate, and the product is obtained after filtration. (yield rate: 96%)

¹ H NMR (400 MHz, Chloroform) δ 7.78 (s, 1H), 7.64 (dd, J = 7.9, 1.9 Hz, 1H), 7.40 (d, J = 7.9 Hz, 1H).

Preparation Example 1-6. Synthesis of intermediate 37-6

[Scheme 1-6]

Intermediate 37-5 (20.0 g, 59.2 mmol) and phenol (55.8 g, 592.9 mmol) were dissolved in dimethylformamide (80 mL), methanesulfonic acid was added, and the mixture was stirred at 60 °C for 12 hours. After completion of the reaction, distilled water is added to precipitate, and the product is obtained after filtration. (yield rate: 81%)

¹ H NMR (400 MHz, DMSO) δ 9.45 (s, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.58 (dd, J = 8.1, 1.8 Hz, 1H), 7.49 (d, J = 1.7) Hz, 1H), 6.92 - 6.87 (m, J = 5.8 Hz, 2H), 6.69 - 6.64 (m, 2H).

Preparation Example 1-7. Synthesis of intermediate 37-7

[Scheme 1-7]

After dissolving 4-vinylphenol (15.0 g, 124.8 mmol), 1,6-dibromohexane (121.8 g, 499.3 mmol) and potassium carbonate (51.76 g, 374.5 mmol) in dimethylformamide (250 mL), 70 Stirred at °C for 24 h. After completion of the reaction, after cooling, extraction with ethyl acetate is used to obtain a product through column chromatography. (yield rate: 79%)

¹ H NMR (400 MHz, Chloroform) δ 7.34 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 6.66 (dd, J = 17.6, 10.9 Hz, 1H), 5.61 ( d, J = 17.6 Hz, 1H), 5.12 (d, J = 10.9 Hz, 1H), 3.96 (t, J = 6.4 Hz, 2H), 3.43 (t, J = 8.6, 4.9 Hz, 2H), 1.94 - 1.87 (m, J = 13.9, 6.9 Hz, 2H), 1.83 - 1.76 (m, 2H), 1.54 - 1.48 (m, 4H).

Preparation Example 1-8. Synthesis of intermediate 37-8

[Scheme 1-8]

Intermediate 37-6 (4.5 g, 8.85 mmol), Intermediate 37-4 (11.0 g, 35.4 mmol) and potassium carbonate (3.67 g, 26.6 mmol) were dissolved in dimethylformamide (20 mL) at 70 °C for 24 hours. stirred while After completion of the reaction, after cooling, extraction with ethyl acetate is used to obtain a product through column chromatography. (yield rate: 70%)

¹ H NMR (400 MHz, Chloroform) δ 7.71 - 7.69 (m, 1H), 7.48 (d, 1H), 7.45 (dd, 1H), 7.26 (d, 1H), 7.18 (d, 2H), 7.13 (s) , 1H), 7.11 (dd, 1H), 6.92 (d, 2H), 4.96 (t, 1H), 3.93 (t, 2H), 3.50 (t, 2H), 3.15 - 3.11 (m, 1H), 2.90 - 2.86 (m, 1H), 2.53 (t, 2H), 2.11 - 2.06 (m, 2H), 1.55 - 1.50 (m, 2H), 1.39 - 1.32 (m, 4H), 0.98 (t, 3H).

Preparation Example 1-9. Synthesis of intermediate 37-9

[Scheme 1-9]

Intermediate 37-6 (27.86 g, 98.4 mmol), Intermediate 37-7 (12.5 g, 25.0 mmol) and potassium carbonate (10.19 g, 73.8 mmol) were dissolved in dimethylformamide (50 mL) at 70 °C for 24 hours. stirred while After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 70%)

¹ H NMR (400 MHz, Chloroform) δ 7.60 - 7.57 (m, 1H), 7.50 - 7.46 (m, J = 4.2, 1.7 Hz, 2H), 7.34 (dd, J = 6.6, 4.7 Hz, 2H), 7.06 (dd, 2H), 6.86 (d, 2H), 6.78 (d, 2H), 6.71 - 6.64 (m, J = 17.6, 10.9 Hz, 1H), 5.62 (dd, J = 17.6, 0.8 Hz, 1H), 5.13 (dd, J = 10.9, 0.7 Hz, 1H), 3.98 (t, J = 6.5 Hz, 2H), 3.94 (t, J = 6.4 Hz, 2H), 1.86 - 1.78 (m, J = 11.9, 6.3 Hz) , 4H), 1.56 - 1.51 (m, J = 7.0, 3.5 Hz, 4H).

Preparation Example 1-10. Synthesis of intermediate 37-10

[Scheme 1-10]

2,7-dibromo-9,9-bis(4-(octyloxy)phenyl)-9H-fluorene (6.0 g, 8.2 mmol), bis(pinacolato)diboron (4.62 g, 18.2 mmol) , PdCl ₂ (dppf) (0.36 g, 0.5 mmol) Potassium acetate (2.31 g, 23.5 mmol) was dissolved in 1,4-dioxane (50 mL), followed by stirring at 80 °C for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 81%)

¹ H NMR (400 MHz, Chloroform) δ 7.81 - 7.74 (m, 3H), 7.12 (d, 2H), 6.73 (d, 2H), 3.88 (t, J = 6.5 Hz, 2H), 1.78 - 1.69 (m) , 2H), 1.32 - 1.25 (m, 20H), 0.87 (t, J = 6.9 Hz, 3H).

Preparation Example 1-11. Synthesis of Formula 37

[Scheme 1-11]

Intermediate 37-10 (0.6 g, 0.73 mmol), 2,7-dibromo-9,9-bis(4-(octyloxy)phenyl)-9H-fluorene (0.43 g, 0.58 mmol), Intermediate 37- 9 (0.06 g, 0.07 mmol), intermediate 37-8 (0.07 g, 0.07 mmol), palladium acetate (0.009 g, 0.04 mmol), tricyclohexylphosphine (0.02 g, 0.07 mmol) tetrabutylammonium hydroxide (3 ml) ) was dissolved in toluene (25 mL), followed by nitrogen bubbling for 30 minutes, stirred at 85 ° C. for 24 hours, bromobenzene (1.0 mL) was added, stirred for 12 hours, and phenylboronic acid (1.0 g) and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent of methanol and acetone 3 : 1 and filtered. The filtered mixture was purified by Soxhlet extraction to obtain the compound. (yield rate: 52%)

<Example 2: Synthesis of compound for organic electronic device of Formula 38>

[Scheme 2]

Preparation Example 2-1. Synthesis of Intermediate 38-1

[Scheme 2-1]

Intermediate 37-1 (10.0 g, 54.6 mmol), pentan-1-amine (5.71 g, 65.6 mmol), Pd ₂ (dba) ₃ (2.5 g 2.7 mmol), sodium tert-butoxide (10.5 g, 109.3 mmol) , tri-tert-Bu-phosphine (1.11 g, 5.46 mmol) was dissolved in toluene (110 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 62%)

1H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.24 - 7.22 (m, 1H), 7.22 - 7.16 (m, J = 10.0 Hz, 2H), 4.29 (t, 1H), 3.11 - 3.07 ( m, 1H), 2.86 - 2.82 (m, 1H), 2.66 - 2.61 (m, J = 7.3 Hz, 2H), 1.53 - 1.46 (m, 2H), 1.43 - 1.37 (m, 2H), 1.36 - 1.30 ( m, 2H), 1.30 (s, 1H), 0.99 (t, 3H).

Preparation Example 2-2. Synthesis of Intermediate 38-2

[Scheme 2-2]

Intermediate 38-1 (6.3 g, 33.3 mmol) and distilled water (35 ml) were added while stirring at 0 °C, and bromine (5.32 g, 33.3 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 73%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.29 (t, 1H), 3.11 - 3.06 (m, 1H), 2.86 - 2.82 (m, 1H), 2.66 - 2.61 (m, J = 7.4 Hz, 2H), 1.67 (s, 1H), 1.52 - 1.46 (m, 2H), 1.42 - 1.36 (m, 2H), 1.35 - 1.28 (m) , 2H), 0.99 (t, 3H).

Preparation 2-3. Synthesis of Intermediate 38-3

[Scheme 2-3]

Intermediate 38-2 (6.5 g, 24.2 mmol) was dissolved in tetrahydrofuran (90 ml), tert -butyllithium (28.58 ml, 2M) was added while stirring at -78 ℃, and stirred at -78 ℃ for 30 minutes. Then, 1,8-dibromooctane (26.57 g, 97.7 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 70%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.29 (t, 1H), 3.34 (t, 2H), 3.11 - 3.07 (m) , 1H), 2.86 - 2.81 (m, 1H), 2.67 (t, 1H), 2.63 (t, 1H), 2.53 (t, 2H), 1.87 - 1.82 (m, 2H), 1.81 (s, 1H), 1.69 - 1.62 (m, 2H), 1.46 - 1.41 (m, 2H), 1.37 - 1.29 (m, 12H), 0.99 (t, 3H).

Preparation Example 2-4. Synthesis of Intermediate 38-4

[Scheme 2-4]

[1,1'-binaphthalene]-2,2'-diol (8.0 g, 27.9 mmol) was dissolved in dichloromethane (190 ml) and bromine (12 g, 75.4 mmol) was added while stirring at -10 °C. After addition, the mixture was stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 96%)

¹ H NMR (400 MHz, Chloroform) δ 7.84 (s, 1H), 7.61 (d, 1H), 7.50 (dd, 1H), 7.36 (d, 1H), 7.29 (dd, 1H), 0.32 (s, 1H) ).

Preparation Example 2-5. Synthesis of Intermediate 38-5

[Scheme 2-5]

Intermediate 38-4 (11.0 g, 24.8 mmol), Intermediate 38-3 (37.7 g, 99.1 mmol) and potassium carbonate (10.27 g, 74.3 mmol) were dissolved in dimethylformamide (50 mL) at 70 °C for 24 hours. stirred while After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 69%)

¹ H NMR (400 MHz, Chloroform) δ 8.05 (s, 1H), 7.69 (dd, 2H), 7.50 (d, 1H), 7.36 (dd, 1H), 7.26 (d, 1H), 7.13 (s, 1H) ), 7.11 (dd, 1H), 4.29 (t, 1H), 4.02 - 3.99 (m, 2H), 3.11 - 3.07 (m, 1H), 2.86 - 2.82 (m, 1H), 2.66 (t, 1H), 2.65 (t, 1H), 2.53 (t, 2H), 1.82 (s, 1H), 1.78 - 1.74 (m, 2H), 1.70 - 1.64 (m, 2H), 1.48 - 1.43 (m, 2H), 1.38 - 1.29 (m, 12H), 0.99 - 0.96 (m, 3H).

Preparation Example 2-6. Synthesis of Intermediate 38-6

[Scheme 2-6]

Intermediate 38-4 (10.0 g, 22.5 mmol), Intermediate 37-7 (25.51 g, 90.1 mmol) and potassium carbonate (9.33 g, 67.5 mmol) were dissolved in dimethylformamide (45 mL) at 70 °C for 24 hours. stirred while After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 73%)

¹ H NMR (400 MHz, Chloroform) δ 7.99 (s, 1H), 7.75 (d, 1H), 7.66 (dd, 1H), 7.48 (d, 1H), 7.42 (dd, 1H), 7.28 (d, 2H) ), 6.87 (d, 2H), 6.66 - 6.60 (m, 1H), 5.49 (dd, 1H), 5.20 (dd, 1H), 4.06 (t, 2H), 4.03 (t, 2H), 1.80 - 1.74 ( m, 2H), 1.64 - 1.58 (m, 2H), 1.35 - 1.28 (m, 4H).

Preparation Example 2-7. Synthesis of Intermediate 38-7

[Scheme 2-7]

2,7-dibromo-9,9-bis(4-((2-ethylhexyl)oxy)phenyl)-9H-fluorene (8.0 g, 109.2 mmol), bis(pinacolato)diboron (8.16) g, 24.2 mmol), PdCl ₂ (dppf) (0.48 g, 0.6 mmol) potassium acetate (3.08 g, 31.3 mmol) was dissolved in 1,4-dioxane (60 mL) and stirred at 80 °C for 24 hours. . After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 82%)

¹ H NMR (400 MHz, Chloroform) δ 7.81 - 7.75 (m, 3H), 7.12 (d, J = 8.9 Hz, 2H), 6.73 (d, J = 8.9 Hz, 2H), 3.77 (d, J = 5.3) Hz, 2H), 1.70 - 1.64 (m, 1H), 1.47 - 1.28 (m, 20H), 0.91 - 0.87 (m, J = 9.7, 5.2 Hz, 6H).

Preparation Example 2-8. Synthesis of formula 38

[Scheme 2-8]

Intermediate 38-6 (0.6 g, 0.73 mmol), 2,7-dibromo-9,9-bis(4-((2-ethylhexyl)oxy)phenyl)-9H-fluorene (0.43 g, 0.58 mmol) ), intermediate 38-5 (0.06 g, 0.07 mmol), intermediate 38-7 (0.08 g, 0.07 mmol), palladium acetate (0.009 g, 0.04 mmol), tricyclohexylphosphine (0.02 g, 0.07 mmol) tetrahydroxide After dissolving butylammonium (3 ml) in toluene (25 mL), nitrogen bubbling was performed for 30 minutes, stirred at 85° C. for 24 hours, bromobenzene (1.0 mL) was added, and stirred for 12 hours, followed by phenylboron Add acid (1.0 g) and stir for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent of methanol and acetone 3 : 1 and filtered. The filtered mixture was purified by Soxhlet extraction to obtain the compound. (yield rate: 51%)

<Example 3: Synthesis of compound for organic electronic device of Formula 39>

[Scheme 3]

Preparation Example 3-1. Synthesis of Intermediate 39-1

[Scheme 3-1]

Intermediate 37-1 (23.0 g, 125.6 mmol), butan-1-ol (9.31 g, 125.6 mmol), and sodium hydride (3.62 g, 150.8 mmol) were dissolved in dimethylformamide (600 mL) and then at 60 ° C. 24 stirred for hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 65%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.24 - 7.22 (m, 1H), 7.22 - 7.17 (m, J = 10.0 Hz, 2H), 4.96 (t, 1H), 3.52 (t) , 2H), 3.15 - 3.10 (m, 1H), 2.90 - 2.85 (m, 1H), 1.58 - 1.53 (m, 2H), 1.52 - 1.46 (m, 2H), 0.99 (t, 3H).

Preparation Example 3-2. Synthesis of Intermediate 39-2

[Scheme 3-2]

Intermediate 39-1 (14.0 g, 79.4 mmol) and distilled water (80 ml) were added while stirring at 0 °C, and bromine (12.69 g, 79.4 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 69%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.96 (t, 1H), 3.52 (t, 2H), 3.15 - 3.11 (m , 1H), 2.90 - 2.86 (m, 1H), 1.58 - 1.53 (m, 2H), 1.50 - 1.45 (m, 2H), 0.99 (t, 3H).

Preparation Example 3-3. Synthesis of Intermediate 39-3

[Scheme 3-3]

Intermediate 39-2 (14.0 g, 54.9 mmol) was dissolved in tetrahydrofuran (200 ml), tert -butyllithium (64.69 ml, 2M) was added while stirring at -78 °C, and stirred at -78 °C for 30 minutes. Then, 1,4-dibromobutane (47.74 g, 221.1 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 74%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.41 (t, 2H) ), 3.15 - 3.10 (m, 1H), 2.90 - 2.85 (m, 1H), 2.53 (t, 2H), 1.89 - 1.83 (m, 2H), 1.72 - 1.66 (m, 2H), 1.60 - 1.54 (m) , 2H), 1.44 - 1.37 (m, 2H), 1.00 (t, 3H).

Preparation 3-4. Synthesis of Intermediate 39-4

[Scheme 3-4]

Intermediate 39-3 (10.0 g, 32.1 mmol), bis(4-bromophenyl)amine (10.51 g, 32.1 mmol), Pd ₂ (dba) ₃ (1.47 g 1.6 mmol), sodium tert-butoxide (6.18 g) , 64.3 mmol), tri-tert-Bu-phosphine (0.65 g, 3.2 mmol) was dissolved in toluene (60 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 75%)

¹ H NMR (400 MHz, Chloroform) δ 7.41 (d, 4H), 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 6.89 (d, 4H), 4.96 (t, 1H) ), 3.57 (t, 2H), 3.31 (t, 2H), 3.15 - 3.11 (m, 1H), 2.90 - 2.85 (m, 1H), 2.53 (t, 2H), 1.72 - 1.67 (m, 2H), 1.64 - 1.56 (m, 4H), 1.49 - 1.44 (m, 2H), 1.00 (t, 3H).

Preparation 3-5. Synthesis of Intermediate 39-5

[Scheme 3-5]

1-bromo-4-vinylbenzene (10.0 g, 54.6 mmol), bis(4-bromophenyl)amine (17.86 g, 54.6 mmol), Pd ₂ (dba) ₃ (2.5 g 2.7 mmol), sodium tert- Butoxide (10.5 g, 109.3 mmol) and tri-tert-Bu-phosphine (1.11 g, 5.5 mmol) were dissolved in toluene (100 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 77%)

1H NMR (400 MHz, Chloroform) δ 7.40 (d, 4H), 7.26 (d, 2H), 7.01 (d, 2H), 6.95 (d, 4H), 6.66 - 6.59 (m, 1H), 5.50 (dd, 1H), 5.21 (dd, 1H).

Preparation Example 3-6. Synthesis of formula 39

[Scheme 3-6]

Intermediate 39-4 (0.58 g, 1.05 mmol), Intermediate 39-5 (0.05 g, 0.12 mmol), 9,10-bis(5-bromo-2-(octyloxy)phenyl)anthracene (0.09 g, 0.12 mmol) ) was dissolved in anhydrous tetrahydrofuran (30 mL), followed by nitrogen bubbling for 10 minutes. After raising the temperature to 40 ℃, 2,2'-bipyridyl (0.4 g, 2.56 mmol) was added, and the temperature was raised to 60 ℃ again. Then, bis (1,5-cyclooctadiene) nickel (0) (0.88 g, 3.2 mmol) and stirred for 2 hours, then bromobenzene (0.8 mL) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent of methanol and acetone in a ratio of 3:1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain the compound. (yield rate: 53%)

<Example 4: Synthesis of compound for organic electronic device of Formula 40>

[Scheme 4]

Preparation Example 4-1. Synthesis of Intermediate 40-1

[Scheme 4-1]

Intermediate 37-1 (23.0 g, 125.6 mmol), hexan-1-ol (12.84 g, 125.6 mmol), and sodium hydride (3.62 g, 150.8 mmol) were dissolved in dimethylformamide (400 mL) at 60 ° C. 24 stirred for hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 56%)

1H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.23 (dd, 1H), 7.22 - 7.17 (m, J = 10.0 Hz, 2H), 4.96 (t, 1H), 3.49 (t, 2H) , 3.15 - 3.11 (m, 1H), 2.90 - 2.86 (m, 1H), 1.61 - 1.55 (m, 2H), 1.41 - 1.36 (m, 2H), 1.35 - 1.29 (m, 4H), 0.99 (t, 3H).

Preparation Example 4-2. Synthesis of Intermediate 40-2

[Scheme 4-2]

Intermediate 40-1 (14.0 g, 68.5 mmol) and distilled water (70 ml) were added while stirring at 0 °C, and bromine (10.96 g, 68.5 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 72%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.15 - 3.11 (m) , 1H), 2.90 - 2.85 (m, 1H), 1.60 - 1.54 (m, 2H), 1.41 - 1.36 (m, 2H), 1.35 - 1.30 (m, 4H), 0.99 (t, 3H).

Preparation Example 4-3. Synthesis of Intermediate 40-3

[Scheme 4-3]

Intermediate 40-2 (14 g, 49.4 mmol) was dissolved in tetrahydrofuran (180 ml), tert -butyllithium (58.28 ml, 2M) was added while stirring at -78 ℃, and stirred at -78 ℃ for 30 minutes. Then, 1,3-dibromopropane (40.2 g, 199.2 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 75%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.40 (t, 2H) ), 3.15 - 3.11 (m, 1H), 2.90 - 2.85 (m, 1H), 2.53 (t, 2H), 2.22 - 2.15 (m, 2H), 1.61 - 1.54 (m, 2H), 1.42 - 1.36 (m) , 2H), 1.35 - 1.29 (m, 4H), 0.99 (t, 3H).

Preparation Example 4-4. Synthesis of Intermediate 40-4

[Scheme 4-4]

Intermediate 40-3 (12.0 g, 36.9 mmol), (4-vinylphenyl)boronic acid (5.46 g, 36.9 mmol), Pd(PPh ₃ ) ₄ (0.64 g, 0.55 mmol), potassium carbonate (25.49 g, 184.5 mmol) ) was dissolved in toluene : ethanol : distilled water (3 : 1 : 1 , 500 ml) and stirred at 85 °C for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 52%)

¹ H NMR (400 MHz, Chloroform) δ 7.29 (d, 2H), 7.26 (d, 1H), 7.15 (d, 2H), 7.13 (s, 1H), 7.11 (dd, 1H), 6.66 - 6.59 (m , 1H), 5.57 - 5.52 (m, 1H), 5.26 (dd, 1H), 4.96 (t, 1H), 3.49 (t, 2H), 3.15 - 3.11 (m, 1H), 2.90 - 2.86 (m, 1H) ), 2.60 (t, 2H), 2.53 (t, 2H), 2.04 - 1.97 (m, 2H), 1.61 - 1.54 (m, 2H), 1.42 - 1.36 (m, 2H), 1.35 - 1.29 (m, 4H) ), 0.99 (t, 3H).

Preparation Example 4-5. Synthesis of Intermediate 40-5

[Scheme 4-5]

1-Bromo-4-vinylbenzene (10.0 g, 54.6 mmol), carbazole (9.13 g, 54.6 mmol), Pd ₂ (dba) ₃ (2.5 g 2.7 mmol), sodium tert-butoxide (10.5 g, 109.3) mmol), tri-tert-Bu-phosphine (1.11 g, 5.5 mmol) was dissolved in toluene (100 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 79%)

1H NMR (400 MHz, Chloroform) δ 7.81 (dd, 2H), 7.57 (dd, 2H), 7.51 (d, 2H), 7.44 (d, 2H), 7.25 (td, 2H), 7.14 (td, 2H) , 6.66 - 6.59 (m, 1H), 5.59 (dd, 1H), 5.30 (dd, 1H).

Preparation Example 4-6. Synthesis of Formula 40

[Scheme 4-6]

Intermediate 40-4 (2.0 g, 5.74 mmol), Intermediate 40-5 (13.91 g, 51.65 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile ( 0.10 g, 0.344 mmol), dissolved in tetrahydrofuran (15 mL), and stirred at 40 °C for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250ml) and filtered to obtain a product. (Yield: 48%)

<Example 5: Synthesis of compound for organic electronic device of Formula 41>

[Scheme 5]

Preparation Example 5-1. Synthesis of Intermediate 41-1

[Scheme 5-1]

Intermediate 37-1 (23.0 g, 125.6 mmol), hexan-1-amine (15.26 g, 150.8 mmol), Pd ₂ (dba) ₃ (5.75 g 6.28 mmol), sodium tert-butoxide (24.15 g, 251.3 mmol) , tri-tert-Bu-phosphine (2.54 g, 12.6 mmol) was dissolved in toluene (250 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 64%)

1H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.23 (dd, 1H), 7.22 - 7.17 (m, J = 10.0 Hz, 2H), 4.29 (t, 1H), 3.11 - 3.07 (m, 1H), 2.86 - 2.81 (m, 1H), 2.66 - 2.60 (m, J = 7.3 Hz, 2H), 1.53 - 1.46 (m, 2H), 1.42 - 1.35 (m, 2H), 1.34 - 1.30 (m, 4H), 1.30 (s, 1H), 0.99 (t, 3H).

Preparation Example 5-2. Synthesis of intermediate 41-2

[Scheme 5-2]

Intermediate 41-1 (14.0 g, 68.9 mmol) and distilled water (70 ml) were added while stirring at 0 °C, and bromine (11.0 g, 68.9 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 72%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.29 (t, 1H), 3.12 - 3.07 (m, 1H), 2.86 - 2.81 (m, 1H), 2.66 - 2.61 (m, J = 7.4 Hz, 2H), 1.67 (s, 1H), 1.52 - 1.46 (m, 2H), 1.41 - 1.35 (m, 2H), 1.35 - 1.31 (m) , 4H), 0.99 (t, 3H).

Preparation Example 5-3. Synthesis of Intermediate 41-3

[Scheme 5-3]

Intermediate 41-2 (14.0 g, 49.6 mmol) was dissolved in tetrahydrofuran (180 ml), tert -butyllithium (22.32 ml, 2M) was added while stirring at -78 ℃, and stirred at -78 ℃ for 30 minutes. Then, 1,3-dibromopropane (40.36 g, 199.9 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 75%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.29 (t, 1H), 3.41 (t, 2H), 3.11 - 3.07 (m) , 1H), 2.86 - 2.82 (m, 1H), 2.66 - 2.61 (m, J = 7.6 Hz, 2H), 2.53 (t, 2H), 2.21 - 2.15 (m, 2H), 1.71 (s, 1H), 1.53 - 1.47 (m, 2H), 1.41 - 1.36 (m, 2H), 1.34 - 1.30 (m, 4H), 0.99 (t, 3H).

Preparation Example 5-4. Synthesis of Intermediate 41-4

[Scheme 5-4]

Intermediate 41-3 (12.0 g, 37.0 mmol), (4-vinylphenyl)boronic acid (5.48 g, 37.0 mmol), Pd(PPh ₃ ) ₄ (0.64 g, 0.55 mmol), potassium carbonate (25.57 g, 185.0 mmol) ) was dissolved in toluene : ethanol : distilled water (3 : 1 : 1 , 500 ml) and stirred at 85 °C for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 52%)

¹ H NMR (400 MHz, Chloroform) δ 7.29 (d, 2H), 7.26 (d, 1H), 7.15 (d, 2H), 7.13 (s, 1H), 7.11 (dd, 1H), 6.66 - 6.60 (m) , 1H), 5.55 (dd, 1H), 5.26 (dd, 1H), 4.29 (t, 1H), 3.11 - 3.07 (m, 1H), 2.86 - 2.81 (m, 1H), 2.63 (t, J = 6.8 Hz, 2H), 2.62 - 2.58 (m, 2H), 2.53 (t, 2H), 2.03 - 1.97 (m, 2H), 1.69 (s, 1H), 1.53 - 1.47 (m, 2H), 1.42 - 1.36 ( m, 2H), 1.34 - 1.30 (m, 4H), 0.99 (t, 3H).

Preparation Example 5-5. Synthesis of intermediate 41-5

[Scheme 5-5]

1-bromo-4-vinylbenzene (10.0 g, 54.6 mmol), diphenylamine (9.24 g, 54.6 mmol), Pd ₂ (dba) ₃ (2.5 g 2.7 mmol), sodium tert-butoxide (10.5 g, 109.3 mmol), tri-tert-Bu-phosphine (1.11 g, 5.5 mmol) was dissolved in toluene (100 mL), followed by stirring at 100 °C for 12 hours. After completion of the reaction, after cooling, extraction with MC is followed to obtain a product through column chromatography. (yield rate: 79%)

1H NMR (400 MHz, Chloroform) δ 7.27 (d, 2H), 7.23 (t, 4H), 7.08 (dd, 4H), 7.05 (d, 2H), 6.95 (t, 2H), 6.66 - 6.60 (m, 1H), 5.51 (dd, 1H), 5.22 (dd, 1H).

Preparation Example 5-6. Synthesis of intermediate 41-6

[Scheme 5-6]

4-Bromopyrimidine (5.87 g, 36.9 mmol), (4-vinylphenyl)boronic acid (5.46 g, 36.9 mmol), Pd(PPh ₃ ) ₄ (0.64 g, 0.55 mmol), potassium carbonate (25.51 g, 184.6 mmol) was dissolved in toluene : ethanol : distilled water (3 : 1 : 1, 500 ml) and stirred at 85 °C for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 57%)

¹ H NMR (400 MHz, Chloroform) δ 9.23 (s, 1H), 8.52 (d, 1H), 7.64 (d, 2H), 7.58 (d, 1H), 7.48 (d, 2H), 6.66 - 6.60 (m , 1H), 5.62 (dd, 1H), 5.33 (dd, 1H).

Preparation Example 5-7. Synthesis of Formula 41

[Scheme 5-7]

In a reactor under nitrogen atmosphere, intermediate 41-4 (2.0 g, 5.74 mmol), intermediate 41-5 (7.03 g, 2.59 mmol), intermediate 41-6 (4.72 g, 2.59 mmol), 2,2-azobis-4- Methoxy-2,4-dimethylvaleronitrile (0.11 g, 0.345 mmol) was dissolved in tetrahydrofuran (3.0 mL) and stirred at 45 °C for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. ( Yield: 60 %)

<Example 6: Synthesis of compound for organic electronic device of Formula 42>

[Scheme 6]

Preparation Example 6-1. Synthesis of Intermediate 42-1

[Scheme 6-1]

Intermediate 37-1 (23.0 g, 125.6 mmol), propan-1-ol (7.55 g, 125.6 mmol), and sodium hydride (3.62 g, 150.8 mmol) were dissolved in dimethylformamide (600 mL) at 60 ° C. 24 stirred for hours. After completion of the reaction, after cooling, after cooling, extraction with ethyl acetate and column chromatography to obtain a product. (yield rate: 71%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (dd, 1H), 7.23 (dd, 1H), 7.22 - 7.16 (m, J = 10.0 Hz, 2H), 4.96 (t, 1H), 3.48 (t, 2H) ), 3.16 - 3.11 (m, 1H), 2.90 - 2.85 (m, 1H), 1.72 - 1.64 (m, 2H), 1.00 (t, 3H).

Preparation Example 6-2. Synthesis of Intermediate 42-2

[Scheme 6-2]

Intermediate 42-1 (14.0 g, 86.3 mmol) and distilled water (85 ml) were added while stirring at 0 °C, and bromine (13.79 g, 86.3 mmol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, after cooling, after cooling, extraction with ethyl acetate and column chromatography to obtain a product. (yield rate: 67%)

¹ H NMR (400 MHz, Chloroform) δ 7.38 (s, 1H), 7.36 (dd, 1H), 7.15 (d, 1H), 4.96 (t, 1H), 3.48 (t, 2H), 3.15 - 3.11 (m , 1H), 2.90 - 2.86 (m, 1H), 1.70 - 1.64 (m, 2H), 1.00 (t, 3H).

Preparation Example 6-3. Synthesis of Intermediate 42-3

[Scheme 6-3]

Intermediate 42-2 (14 g, 58.1 mmol) was dissolved in tetrahydrofuran (200 ml), tert -butyllithium (68.46 ml, 2M) was added while stirring at -78 °C, and stirred at -78 °C for 30 minutes. Then, 1,4-dibromobutane (50.52 g, 234.0 mmol) was added and stirred at room temperature for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 69%)

¹ H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 4.96 (t, 1H), 3.47 (t, 2H), 3.36 (t, 2H) ), 3.15 - 3.10 (m, 1H), 2.90 - 2.85 (m, 1H), 2.53 (t, 2H), 1.86 - 1.81 (m, 2H), 1.73 - 1.66 (m, 4H), 0.99 (t, 3H) ).

Preparation Example 6-4. Synthesis of Intermediate 42-4

[Scheme 6-4]

Intermediate 42-3 (12.0 g, 40.4 mmol), methacrylic acid (3.48 g, 40.4 mmol), and sodium hydride (1.16 g, 48.5 mmol) were dissolved in dimethylformamide (200 mL) at 60 °C for 24 hours. stirred. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 66%)

1H NMR (400 MHz, Chloroform) δ 7.26 (d, 1H), 7.13 (s, 1H), 7.11 (dd, 1H), 6.06 (s, 1H), 5.49 (s, 1H), 4.96 (t, 1H) , 4.14 (t, 2H), 3.48 (t, 2H), 3.16 - 3.11 (m, 1H), 2.90 - 2.86 (m, 1H), 2.53 (t, 2H), 2.01 (s, 3H), 1.72 - 1.61 (m, 6H), 1.00 (t, 3H).

Preparation Example 6-5. Synthesis of Formula 42

[Scheme 6-5]

Intermediate 42-4 (4.0 g, 13.2 mmol), 1,2,3,4,5-pentafluoro-6-vinylbenzene (2.57 g, 13.2 mmol), 2,2-azobis- It was dissolved in 4-methoxy-2,4-dimethylvaleronitrile (0.25 g, 0.794 mmol) and tetrahydrofuran (5 mL) and stirred at 45 °C for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (Yield: 54 %)

<Preparation Example 7: Synthesis of Comparative Compound 1>

[Scheme 7]

Preparation Example 7-1. Synthesis of Comparative Example 1-1

[Scheme 7-1]

1,6-dibromohexane (20.0 g, 82.0 mmol), (4-vinylphenyl)boronic acid (12.13 g, 82.0 mmol), Pd(PPh ₃ ) ₄ (1.42 g, 1.23 mmol), potassium carbonate (56.65) g, 409.9 mmol) was dissolved in toluene : ethanol : distilled water (3 : 1 : 1 , 1000 ml) and stirred at 85 °C for 24 hours. After completion of the reaction, after cooling, extraction with ethyl acetate is performed, and then the product is obtained through column chromatography. (yield rate: 73%)

¹ H NMR (400 MHz, Chloroform) δ 7.29 (d, 2H), 7.14 (d, 2H), 6.66 - 6.60 (m, 1H), 5.55 (dd, 1H), 5.26 (dd, 1H), 3.34 (t) , 2H), 2.58 (t, 2H), 1.88 - 1.82 (m, 2H), 1.68 - 1.61 (m, 2H), 1.35 - 1.29 (m, 4H).

Preparation Example 7-2. Synthesis of Comparative Example 1-2

[Scheme 7-2]

2,7-dibromo-9H-fluorene (9.0 g, 27.8 mmol), Comparative Example 1-1 (15.59 g, 58.3 mmol), potassium hydroxide (6.23 g, 111.1 mmol), potassium iodide (0.69 g, 4.2) mmol) was dissolved in toluene (70 ml) and stirred at room temperature for 12 hours. After completion of the reaction, it is cooled, extracted with MC, and the product is obtained through column chromatography. (yield rate: 76%)

¹ H NMR (400 MHz, Chloroform) δ 7.78 (s, 1H), 7.70 (d, 1H), 7.59 (dd, 1H), 7.31 (d, 2H), 7.13 (d, 2H), 6.66 - 6.60 (m , 1H), 5.54 (dd, 1H), 5.25 (dd, 1H), 2.58 (t, 2H), 1.93 (t, 2H), 1.70 - 1.63 (m, 2H), 1.44 - 1.39 (m, 2H), 1.38 - 1.34 (m, 4H).

Preparation Example 7-3. Synthesis of Comparative Compound 1

[Scheme 7-3]

2,7-dibromo-9,9-dioctyl-9H-fluorene (1.42 g, 2.58 mmol) and Comparative Example 1-2 (0.2 g, 0.28 mmol) were mixed with anhydrous tetrahydrofuran (60 mL) under a nitrogen stream. ), followed by nitrogen bubbling for 10 minutes. After raising the temperature to 40 °C, 2,2'-bipyridyl (0.90 g, 5.74 mmol) was added, and the temperature was raised to 60 °C again, followed by bis(1,5-cyclooctadiene)nickel(0)(1.97 g). , 7.18 mmol) and stirred for 2 hours, bromobenzene (1 mL) was added and stirred for 12 hours. After completion of the reaction, it was precipitated in a solvent of methanol and acetone in a ratio of 3:1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain Comparative Compound 1. (yield rate: 66%)

<Experimental Example 1: Comparative analysis of crosslinking temperature and solvent resistance according to Compound 37 to Compound 42 and Comparative Compound 1>

A polymer material prepared according to Preparation Examples 1 to 6, a compound containing Chemical Formulas 37 to 42, and Comparative Compound 1 prepared according to Preparation Example 7 were dissolved in 1.0 wt% (chlorobenzene) and spin-coated at 1000 rpm for 60 seconds. After crosslinking on a hot plate at 50°C to 200°C for about 30 minutes, immersed in chlorobenzene and taken out after 10 minutes, solvent resistance was measured by comparing absorbance intensity before and after crosslinking, and the results are shown in Table 1 below. .

Referring to Table 1, it was confirmed that the compounds for organic electronic devices of Compounds 37 to 42 according to an exemplary embodiment of the present invention had high solvent resistance even at low temperature crosslinking compared to Comparative Compound 1.

Device Examples 1 to 9: Manufacturing of an organic electroluminescent device as an organic electronic device

PEDOT (poly(styrene sulfonate)-doped poly(3,4-ethylenedioxy thiophene) on ITO (indium-tin oxide)-patterned transparent electrode substrate treated with UV/ozone after washing for 30 minutes with acetone and isopropanol, respectively. : After coating Bayer's Batron P4083) to a thickness of 600 Å, baking was performed for about 1 hour at 180° C. to form a hole injection layer, by dissolving Chemical Formulas 37 to 39 in dichlorobenzene on the hole injection layer A thin film was formed after spin coating and crosslinking for about 30 minutes at 50° C. to 135° C. The thickness of the thin film was formed by controlling the concentration and spin speed of the solution to form a 300 Å thin film. TPBi (300 Å), LiF (5 Å), and Al (1000 Å) were sequentially deposited to form a cathode and encapsulated to form an organic electroluminescent device while maintaining the vacuum level below 4×10 ^-6 torr using When the LiF and Al deposition, the film thickness and the film growth rate were controlled by using a crystal sensor.The structure of the organic electroluminescent device thus fabricated was ITO/PEDOT:PSS (600 Å)/emission layer. Compound (300 Å)/TPBi (300 Å)/LiF (5 Å)/Al (1500 Å), and the light emitting area was 6 mm ^2. The crosslinking temperature and the light emitting layer compound used according to Device Examples 1 to 9 were as follows It is summarized in Table 2.

Device Comparative Examples 1 to 3: Manufacturing of an organic electroluminescent device which is an organic electronic device

An organic electroluminescent device was prepared in the same manner as in Device Example except that Comparative Compound 1 of Comparative Example 1 was used as the light emitting layer compound instead of the compound of Example, and the crosslinking temperature according to Device Comparative Examples 1 to 3 was as follows. It is summarized in Table 2.

<Experimental Example 2: Characteristics analysis of organic light emitting device>

The characteristics of the organic light emitting devices manufactured according to Device Examples 1 to 9 and Device Comparative Example 1 to Device Comparative Example 3 were analyzed, and the results of luminous efficiency and driving voltage are shown in Table 2 below.

Referring to Table 2, Device Examples 1 to 9, which are organic light emitting devices according to an exemplary embodiment of the present invention, are compared to Device Comparative Examples 1 to 3 by a high crosslinking temperature through a low temperature crosslinking temperature. It was confirmed that high luminous efficiency and improved low driving voltage were realized by improving the problems.

Therefore, the compound for an organic electronic device according to an exemplary embodiment of the present invention and the organic electronic device including the same can be cross-linked at a low temperature, thereby improving solvent resistance to organic solvents and improving device characteristics through additional multilayer thin film formation.

In the above, although the present invention has been described by way of limited examples, the present invention is not limited thereto, and the technical idea of the present invention and the claims to be described below by those of ordinary skill in the art to which the present invention pertains It goes without saying that various modifications and variations are possible within the equivalent range of the range.

Claims (11)

A compound for an organic electronic device represented by the following structural formula 1:
[Structural Formula 1]

In Structural Formula 1,
Wherein x, y and z are the number of repeating units,
The ratio of x, y and z is x: y + z = 0.01 to 0.99: 0.99 to 0.01,
n is 1 to 4,
R ¹ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group , substituted or unsubstituted C1 to C30 heteroarylene group, substituted or unsubstituted C1 to C30 alkoxylylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocycloalkoxyylene a group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group,
R ² is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group , substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted C1 to C30 heterocycloalkoxy group, substituted Or an unsubstituted C6 to C30 aryloxy group, or a substituted or unsubstituted C1 to C30 heteroaryloxy group,
X ¹ is an oxygen atom or

is,
Ar ¹ is each a substituted C6 to C60 arylene group, or a substituted C2 to C60 heteroarylene group,
Ar ² and Ar ³ are the same as or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 arylene group, or a substituted or unsubstituted C2 to C60 heteroarylene group,
The “*” is a connection point. A compound for an organic electronic device represented by the following Structural Formula 2:
[Structural Formula 2]

In Structural Formula 2,
Wherein k, l and m are the number of repeating units,
The ratio of k, l and m is k: l + m = 0.01 to 0.99: 0.99 to 0.01,
n is 1 to 4,
P ¹ is

, ,

and

ego,
R ³ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group , substituted or unsubstituted C1 to C30 heteroarylene group, substituted or unsubstituted C1 to C30 alkoxylylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted or unsubstituted C1 to C30 heterocycloalkoxyylene a group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group,
wherein R ⁴ to R ⁷ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C1 to C30 heterocycloalkyl group , substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkoxy group, substituted or unsubstituted a cyclic C1 to C30 heterocycloalkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, or a substituted or unsubstituted C1 to C30 heteroaryloxy group;
The X ² to X ⁴ are the same as or different from each other, and each independently an oxygen atom or

is,
The Q ¹ and Q ² are the same as or different from each other, and each independently

,

,

and

ego,
wherein R ⁸ to R ¹² are the same as or different from each other, and each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least any of R ⁸ to R ¹² One is a fluorine atom, or a substituted or unsubstituted C1 to C30 fluoroalkyl group,
wherein R ¹³ and R ¹⁴ are the same as or different from each other, and are each independently a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C1 to C30 heterocycloalkylene group , substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C1 to C30 heteroarylene group, substituted or unsubstituted C1 to C30 alkoxyylene group, substituted or unsubstituted C3 to C30 cycloalkoxyylene group, substituted Or an unsubstituted C1 to C30 heterocycloalkoxyylene group, a substituted or unsubstituted C6 to C30 aryloxyylene group, or a substituted or unsubstituted C1 to C30 heteroaryloxyylene group,
wherein X ⁵ and X ⁶ are the same as or different from each other, and each independently an oxygen atom or

ego,
Ar ⁴ To Ar ⁶ is a substituted or unsubstituted C6 to C60 arylene group, or a substituted or unsubstituted C2 to C60 heteroarylene group,
The “*” is a connection point. The method according to claim 1,
The Ar ¹ to Ar ³ is a compound for an organic electronic device as follows:
The Ar ¹ is

,

,

,

,

,

,

,

,

or

ego,
remind "

" is the point of substitution,
wherein X ⁷ is an oxygen atom, a sulfur atom, or

ego,
The Ar ² and Ar ³ are the same as or different from each other, and each independently

,

,

,

,

,

,

,

,

,

,

,

,

,

,

or

ego,
wherein X ⁸ and X ⁹ are the same as or different from each other, and each independently an oxygen atom, a sulfur atom or

is,
said R ¹⁵ to R ⁵⁹ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C1 to C30 heteroaryl group.
3. The method according to claim 2,
The Ar ⁴ to Ar ⁶ is a compound for an organic electronic device as follows:
The Ar ⁴ To Ar ⁶ Are the same as or different from each other, and each independently

,

,

,

,

,

,

,

or

to be.
The method according to claim 1,
In Structural Formula 1

is a compound for an organic electronic device that is one selected from the following formulas 1 to 18:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]
.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

. 3. The method according to claim 2,
In Structural Formula 2

is a compound for an organic electronic device that is one selected from the following formulas 19 to 26:
[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

. The method according to claim 1,
In Structural Formula 1, Ar ² and Ar ³ are each independently selected from the following Chemical Formulas 27 to 32 for an organic electronic device compound:
[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

.
3. The method according to claim 2,
In Structural Formula 2, Q ¹ and Q ² are each independently selected from the following Chemical Formulas 33 to 36 Compounds for organic electronic devices:
[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

. The method according to claim 1,
The Structural Formula 1 is a compound for an organic electronic device which is one selected from the following Chemical Formulas 37 to 39:
[Formula 37]

[Formula 38]

[Formula 39]

. 3. The method according to claim 2,
The Structural Formula 2 is a compound for an organic electronic device which is one selected from the following Chemical Formulas 40 to 42:
[Formula 40]

[Formula 41]

[Formula 42]

In the organic electronic device comprising an organic layer,
The organic layer is an organic electronic device comprising the compound for an organic electronic device of any one of claims 1 to 10.