Compound for organic electric element, organic electric element using same, and electronic device therefor

Abstract

The present invention provides: a novel compound which can improve the luminous efficiency, stability, and lifespan of an element; an organic electrical element using the compound; and an electronic device including the organic electrical element.

Description

[0001] Description of the case

[0002] This application is a divisional application of patent application No. 202180025783.7, filed on April 8, 2021, with the invention name “Compounds for organic electrical elements, organic electrical elements using the same and electronic devices thereof”, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to a compound for an organic electric element, an organic electric element using the compound, and an electronic device thereof. Background Art

[0004] Flat panel display devices play a very important role in supporting the advanced image information society based on the Internet, which has shown rapid growth in recent years. In particular, organic electroluminescent devices (organic EL devices) that are self-emitting types and can be driven at low voltage have excellent viewing angles and contrast compared to liquid crystal displays (LCDs) that are the mainstream of flat panel display devices, and do not require backlights, so they can be lightweight and thin, and have advantages in power consumption. In addition, due to their fast response speed and wide color reproduction range, they have attracted much attention as next-generation display devices. Typically, organic EL devices are formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light-emitting region, and a metal electrode (cathode). In this case, in addition to the light-emitting layer (EML), the organic thin film includes a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL) or an electron injection layer (EIL), and due to the light-emitting characteristics of the light-emitting layer, further includes an electron blocking layer (EBL) or a hole blocking layer (HBL) and a light-emitting auxiliary layer. When an electric field is applied to an organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode, and the injected holes and electrons pass through the hole transport layer and the electron transport layer, respectively, and recombine in the light-emitting layer to form luminescent excitons. The formed luminescent excitons emit light when they transition to the ground state. At this time, in order to increase the efficiency and stability of the luminescent state, a luminescent dye (guest) is also doped into the light-emitting layer (host). In order to use such organic electronic devices in various display media, the service life of the elements is more important than any other case, and various studies are conducted to increase the service life of organic electronic elements. In particular, for the excellent service life characteristics of organic electrical devices, various studies have been conducted on organic materials inserted in buffer layers (such as hole transport layers or light-emitting auxiliary layers), and in view of this, it is necessary to have high uniformity and low crystallinity when forming a thin film after deposition, while providing materials for hole injection layers and hole transport layers with high hole transport properties from the anode to the organic layer.

[0005] It is necessary to develop materials for the hole injection layer and the hole transport layer that not only have stable properties (i.e., high glass transition temperature) with respect to the Joule heat generated during device operation, but also delay the penetration and diffusion of metal oxides from the anode electrode (ITO), which is one of the reasons for shortening the service life of organic electrical devices. In addition, it is reported that hole transport layer materials with low glass transition temperatures greatly affect the service life of the device due to the property that the uniformity of the film surface is destroyed during device operation. In addition, in the formation of OLED devices, the deposition method is the mainstream, and materials that can withstand this deposition method for a long time, i.e., materials with strong heat resistance characteristics, are needed.

[0006] In particular, there is an urgent need to overcome the problems of power consumption and lifespan because the main challenges to overcome for organic light emitting diodes are enlarged in the panel size of mobile phones and tablet PCs.

[0007] However, as hole transport layer materials, it is difficult to simultaneously overcome the driving voltage and service life. The reason is that in order to reduce the driving voltage, in most cases, materials with excellent hole transport ability (i.e., high hole mobility) have an electron-rich planar structure. For example, naphthyl, fluorene, and phenanthrene.

[0008] However, when a compound having the above structure is introduced as a substituent into a hole transport material, the hole mobility increases to a certain amount and has a good effect on the service life, but if the amount introduced into the molecule is increased to achieve the low-voltage driving target required in the current industry, the driving voltage is reduced and low-voltage driving is feasible, but the service life characteristics deteriorate rapidly.

[0009] The reason for this is that for molecules in which electron-rich planar structures are excessively introduced, holes are trapped between the sheet structures and stabilized when a constant current is continuously supplied during device life evaluation, which reduces hole mobility and ultimately increases the driving voltage for applying the constant current, leading to a sharp deterioration in device life. This is expressed by the following formula.

[0010]

[0011] (J = space charge limited current, ε = tolerance, μ = mobility coefficient, θ = charge trapping coefficient (free carriers / total carriers), V = voltage, d = thickness)

[0012] As the number of free carriers decreases due to trapping, the θ value decreases. Consequently, in current-driven organic light-emitting devices that require a constant current, the driving voltage increases, which can have a very detrimental impact on the device's lifespan. Therefore, as described above, the introduction of electron-rich sheet structures that increase hole mobility beyond a certain amount will adversely affect the device's lifespan, making it unlikely that the drive voltage can be reduced by using them.

[0013] Therefore, the present inventors confirmed that compounds substituted with deuterium show many thermodynamic behaviors compared to unsubstituted compounds, and among these thermodynamic properties, when an iridium compound is substituted with deuterium, the properties vary depending on the differences in carbon, hydrogen, and carbon and deuterium bond lengths, and compared to compounds not substituted with deuterium, compounds containing deuterium can have higher luminous efficiency due to weakened intermolecular van der Waals forces generated by shorter bond lengths.

[0014] However, research on methods for reducing driving voltage by deuterium substitution, that is, increasing the hole transport mobility of hole transport materials, has not been sufficient, and no prior art has been reported to demonstrate this effect based on a specific deuterium substitution rate. In addition, the disadvantage of the commonly reported general deuterium substitution methods is that it is difficult to control the substitution rate. Summary of the Invention

[0015] In order to solve the problems of the above-mentioned background art, in the present invention, deuterium is substituted into an amine-based compound having a long service life at a specific ratio of 74% to 98%, thereby completing a device having a long service life, so as to realize a long-life device, which is a characteristic required for an organic electrical device.

[0016] Therefore, an object of the present invention is to provide a compound deuterated at a specific ratio, an organic electric device using the compound, and an electronic device having the organic electric device.

[0017] [Technical solution]

[0018] The present invention provides compounds represented by formula A that are deuterated by 74% to 98%.

[0019] Formula A

[0020]

[0021] In another aspect, the present invention provides a method for preparing a deuterated compound represented by Formula A.

[0022] In another aspect, the present invention provides organic electric elements and electronic devices comprising the compound represented by formula A.

[0023] [Effects of the Invention]

[0024] By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the element can be achieved, and the color purity and service life of the element can be greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figures 1 to 3 is an exemplary view of an organic electroluminescent device according to the present invention.

[0026] Figure 4 Formulas according to aspects of the present invention are shown.

[0027] 100, 200, 300: organic electrical element 110: first electrode

[0028] 120: hole injection layer 130: hole transport layer

[0029] 140: Light-emitting layer 150: Electron transport layer

[0030] 160: electron injection layer 170: second electrode

[0031] 160: Electron transport layer 170: Electron injection layer

[0032] 180: Light efficiency enhancement layer 210: Buffer layer

[0033] 220: Light-emitting auxiliary layer 320: First hole injection layer

[0034] 330: First hole transport layer 340: First light emitting layer

[0035] 350: First electron transport layer 360: First charge generation layer

[0036] 361: Second charge generation layer 420: Second hole injection layer

[0037] 430: Second hole transport layer 440: Second light-emitting layer

[0038] 450: Second electron transport layer CGL: Charge generation layer

[0039] ST1: First stack ST2: Second stack DETAILED DESCRIPTION

[0040] Hereinafter, some embodiments of the present invention will be described in detail.In addition, in the following description of the present invention, when a detailed description of known functions and configurations incorporated herein may make the subject matter of the present invention rather unclear, the detailed description will be omitted.

[0041] In addition, when describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used herein. Each of these terms is not used to limit the nature, order, or sequence of the corresponding component, but is only used to distinguish the corresponding component from other components. It should be noted that if a component is described as being "connected," "coupled," or "connected" to another component, the component may be directly connected or connected to the other component, but another component may be "connected," "coupled," or "connected" between the components.

[0042] As used in the specification and appended claims, unless otherwise stated, the following terms have the following meanings.

[0043] Unless otherwise stated, the term "halo" or "halogen" as used herein includes fluorine, bromine, chlorine, or iodine.

[0044] Unless otherwise indicated, the term "alkyl" or "alkyl group" as used herein has single bonds of 1 to 60 carbon atoms and means a saturated aliphatic functional group, including a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group (alicyclic), a cycloalkyl group substituted by an alkyl group, or an alkyl group substituted by a cycloalkyl group.

[0045] Unless otherwise specified, the term "alkenyl" or "alkynyl" as used herein has a double bond or triple bond of 2 to 60 carbon atoms, but is not limited thereto, and includes straight chain or branched chain groups.

[0046] Unless otherwise specified, the term "cycloalkyl group" as used herein means an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.

[0047] Unless otherwise specified, the term "alkoxy," "alkoxy group," or "alkyloxy" as used herein means an oxy group attached to an alkyl group having 1 to 60 carbon atoms, but is not limited thereto.

[0048] Unless otherwise specified, the term "aryloxy group" or "aryloxy group" as used herein means an oxy group is attached to an aryl group having 6 to 60 carbon atoms, but is not limited thereto.

[0049] Unless otherwise specified, the terms "aryl group" and "arylene group" used in the present invention each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a monocyclic or polycyclic aromatic group, and includes aromatic rings formed by connecting or reacting adjacent substituents.

[0050] For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

[0051] The prefix "aryl" or "ar" means a group substituted with an aryl group. For example, arylalkyl can be an alkyl substituted with an aryl group, and arylalkenyl can be an alkenyl substituted with an aryl group, and the group substituted with an aryl group has the number of carbon atoms as defined herein.

[0052] In addition, when the prefix is named sequentially, it means that the substituents are listed in the order in which they are first described. For example, arylalkoxy means an alkoxy group substituted by an aryl group, alkoxycarbonyl means a carbonyl group substituted by an alkoxy group, and arylcarbonylalkenyl also means an alkenyl group substituted by an arylcarbonyl group, wherein the arylcarbonyl group can be a carbonyl group substituted by an aryl group.

[0053] Unless otherwise specified, the term "heterocyclic group" as used herein contains one or more heteroatoms, has 2 to 60 carbon atoms, but is not limited thereto, includes any of monocyclic and polycyclic rings, and may include heteroaliphatic rings and heteroaromatic rings. In addition, it may also combine with adjacent groups to form a heterocyclic group.

[0054] Unless otherwise specified, the term "heteroatom" as used herein means at least one of N, O, S, P or Si.

[0055] In addition, the term "heterocyclic group" may include a ring containing SO2 instead of carbon constituting the ring. For example, the "heterocyclic group" includes the following compounds.

[0056]

[0057] Unless otherwise specified, the term "fluorenyl group" or "fluorenylene group" as used herein means a monovalent or divalent functional group in which R, R' and R" in the following structure are all hydrogen, and the term "substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', R" is a substituent other than hydrogen, and includes those in which R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded.

[0058]

[0059] As used herein, the term "spiro compound" has "spiro connection", and spiro connection means a connection in which two rings share only one atom. In this case, the atom shared by the two rings is called a "spiro atom", and these compounds are respectively called "monospiro-", "dispiro-" and "trispiro-" according to the number of spiro atoms in the compound.

[0060] Unless otherwise specified, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "aliphatic cyclo" as used herein means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

[0061] Unless otherwise specified, the term "ring" as used herein means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, or a condensed ring formed by a combination thereof, and includes a saturated ring or an unsaturated ring.

[0062] In addition to the heterocompounds mentioned above, other heterocompounds or heterogroups contain, but are not limited to, one or more heteroatoms.

[0063] In addition, unless otherwise specified, the term "substituted or unsubstituted" as used herein means substituted by one or more substituents selected from deuterium, halogen, amino group, nitrile group, nitro group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylamine group, C1-C 20 Alkylthiophene group, C6-C 20 Arylthiophene group, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl group, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, deuterium-substituted C6-C 20 Aryl group, C8-C 20 Arylene groups, silane groups, boron groups, germanium groups and C2-C 20 Heterocyclic groups, but not limited to these substituents.

[0064] In addition, unless otherwise specified, the definitions of substituents defined by indices in the formulae used in the present invention are the same as those in the following formulae.

[0065]

[0066] Here, when a is an integer of 0, the substituent R 1 Not present, when a is an integer of 1, the only substituent R 1 When a is an integer of 2 or 3, each of the carbon atoms constituting the benzene ring is bonded to the following bond: 1 They may be the same as or different from each other, and when a is an integer of 4 to 6, they are bonded to the carbon of the benzene ring in a similar manner, but indication of hydrogen bonded to the carbon forming the benzene ring is omitted.

[0067]

[0068] As used herein, the term "deuterated" refers to a compound or moiety in which deuterium is present at 100 times or more its natural abundance level.

[0069] As used herein, the term "perdeuterated" refers to a compound or group in which all hydrogens have been replaced by deuterium. The term perdeuterated is synonymous with "100% deuterated."

[0070] As used herein, the term "deuterated acid" refers to a compound that is capable of ionizing to donate deuterium ions to a Bronsted base. As used herein, a deuterium-acid does not contain ionizable hydrogen.

[0071] Hereinafter, a compound according to aspects of the present invention and an organic electric element including the compound will be described.

[0072] The present invention is a method for reducing driving voltage by using a material with good service life without introducing a flaky molecular structure that adversely affects service life, and provides a method for reducing driving voltage by using a method of substituting deuterium at an appropriate ratio.

[0073] When substituted with deuterium, the zero-point energy, or ground-state energy, decreases, and as the deuterium-carbon bond length becomes shorter than the hydrogen-carbon bond length, the molecular core volume decreases. Consequently, the electric polarization can be reduced, and by weakening intermolecular interactions, the film volume can be increased. This property can reduce the crystallinity of the film, i.e., produce an amorphous state, and this is often achieved very efficiently, which is essential for increasing the lifespan and driving characteristics of OLEDs.

[0074] In addition, when a film is formed with a deuterium-substituted compound, the film is formed in an amorphous glass state, which greatly affects the hole mobility of the film, and this amorphous glass state can reduce grain boundaries through isotropic and uniform properties, thereby accelerating the flow of charges, that is, hole mobility.

[0075] The present invention provides compounds represented by formula A that are deuterated by 74% to 98%.

[0076] Formula A

[0077]

[0078] In Formula A, Formula a, and Formula b, each symbol can be defined as follows.

[0079] 1)L 1 , L 2 and L 3 Each independently selected from a single bond; C6-C 60 Arylene group; Fluorenylene group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; and C2-C 60 heterocyclic groups;

[0080] If L 1 , L2 and L 3 are arylene groups, which may preferably be C6-C 30 Arylene groups, more preferably C6-C 24 Arylene groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0081] If L 1 , L 2 and L 3 are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, dibenzothiophene, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0082] If L 1 , L 2 and L 3 are fused ring groups, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0083] 2)Ar 1 and Ar 2 Each independently selected from C6-C 60 Aryl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 60 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 aryloxy groups;

[0084] -L"-N(Ar a )(Ar b ); a substituent represented by formula a; and a substituent represented by formula b;

[0085] If Ar 1 and Ar 2 are aryl groups, which may preferably be C6-C30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0086] If Ar 1 and Ar 2 are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0087] If Ar 1 and Ar 2 are fused ring groups, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0088] If Ar 1 and Ar 2 are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0089] If Ar 1 and Ar 2 are alkoxy groups, which may preferably be C1-C 24 Alkoxy group.

[0090] If Ar 1 and Ar 2 are aryloxy groups, which may preferably be C6-C 24 Aryloxy group.

[0091]

[0092] 3)Ar 3 Selected from C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 60Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; -L"-N(Ar a )(Ar b );

[0093] If Ar 3 is an aryl group, which may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0094] If Ar 3 is a heterocyclic group, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0095] If Ar 3 is a fused ring group, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0096] If Ar 3 is an alkyl group, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0097] If R 3 is an alkoxy group, which may preferably be C1-C 24 Alkoxy group.

[0098] If R 3 is an aryloxy group, which may preferably be C6-C 24 Aryloxy group.

[0099] 4) R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2"、R 3" and R 4" are each independently selected from hydrogen; deuterium; halogen; cyano group; nitro group; C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; and -L"-N(Ar a )(Ar b ); or if a', b', c', d', a", b", c" and d" are 2 or greater, multiple a', b', c', d', a", b", c" and d" are the same or different, multiple adjacent R 1' , or multiple R 2' , or multiple R 3' , or multiple R 4' , or multiple R 1" , or multiple R 2" , or multiple R 3" or more and R 4" may be bonded to each other to form a ring.

[0100] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are aryl groups, which may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0101] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0102] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are fused ring groups, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0103] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0104] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are alkoxy groups, which may preferably be C1-C 24 Alkoxy group.

[0105] If R 1' 、R 2' 、R 3' 、R 4' 、R 1" 、R 2" 、R 3" and R 4" are aryloxy groups, which may preferably be C6-C 24 Aryloxy group.

[0106] 5) a' and b' are each independently an integer from 0 to 5, c', d', a", b", c" and d" are each independently an integer from 0 to 4,

[0107] 6) Any one of * is bonded to L of formula A 2 or L 3 ,

[0108] 7) wherein L" are each independently selected from a single bond; C6-C 60 Arylene group; Fluorenylene group; C3-C 60 Aliphatic ring and C6-C 60 A fused ring group of an aromatic ring; and a C2-C 60 Heterocyclic group; and wherein Ar a and Ar b Each independently selected from C6-C 60 Aryl group; Fluorenyl group; C3-C 60 Aliphatic ring and C6-C 60 A fused ring group of an aromatic ring; and a C2-C 60 heterocyclic groups;

[0109] Wherein if L" is an arylene group, it may preferably be C6-C 30 Arylene groups, more preferably C6-C 24 Arylene groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0110] Wherein if L" is a heterocyclic group, it may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, dibenzothiophene, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0111] If L" is a fused ring group, it may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0112] If Ar a and Ar b are aryl groups, which may preferably be C6-C 30Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0113] If Ar a and Ar b are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0114] If Ar a and Ar b are fused ring groups, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0115] 8) wherein the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, condensed ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group may be substituted by one or more substituents selected from deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1-C 20 Alkylthio group; C1-C 20 Alkoxy group; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C6-C 20 Aryl group; deuterium-substituted C6-C 20 Aryl group; Fluorenyl group; C2-C 20 Heterocyclic group; C3-C 20 Cycloalkyl group; C7-C 20 Arylalkyl group; and C8-C 20 Arylalkenyl group; and -L"-N(Ar a )(Ar b ); In addition, the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term "ring" means a C3-C 60 Aliphatic ring or C6-C 60 Aromatic ring or C2-C 60 a heterocyclic group or a condensed ring formed by combining them.

[0116] Furthermore, the present invention includes wherein Ar 3 A compound represented by formula Ar-1 or formula Ar-2.

[0117]

[0118] Each symbol can be defined as follows.

[0119] 1) * means L bonded to formula A 1 location,

[0120] 2)X 1 O, S, NR a or CR b R c ,

[0121] The condition is that when # is bonded to X 1 When X 1 It is N,

[0122] 3)Y 3 and Y 4 Each is independently a single bond, O, S, NR d or CR e R f ,

[0123] The condition is that when # is bonded to Y 3 When Y 3 It is N,

[0124] 4) R a 、R b 、R c 、R d 、R e and R f Each independently selected from C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 heterocyclic group; or R a 、R b 、R c 、R d 、R e and R f Bonded to an adjacent group to form a ring.

[0125] If R a 、Rb 、R c 、R d 、R e and R f are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0126] If R a 、R b 、R c 、R d 、R e and R f are alkoxy groups, which may preferably be C1-C 24 Alkoxy group.

[0127] If R a 、R b 、R c 、R d 、R e and R f are aryloxy groups, which may preferably be C6-C 24 Aryloxy group.

[0128] If R a 、R b 、R c 、R d 、R e and R f are aryl groups, which may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0129] If R a 、R b 、R c 、R d 、R e and R f are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0130] 5) Ring A and Ring B are each independently selected from C6-C 60Aryl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; and C3-C 60 Aliphatic ring and C6-C 60 A fused aromatic ring group; or ring A and ring B may be R 21 replace.

[0131] Wherein if ring A and ring B are aryl groups, they may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0132] Wherein if ring A and ring B are heterocyclic groups, they may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0133] If ring A and ring B are fused ring groups, they may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0134] 6)R 11 、R 12 、R 13 、R 14 and R 21 are each independently selected from hydrogen; deuterium; halogen; cyano group; C6-C 60 Aryl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; and -L"-N(Ar a )(Ar b ); or R 11 、R 12、R 13 、R 14 and R 21 Bonded to an adjacent group to form a ring.

[0135] If R 11 、R 12 、R 13 、R 14 and R 21 are aryl groups, which may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0136] If R 11 、R 12 、R 13 、R 14 and R 21 are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0137] If R 11 、R 12 、R 13 、R 14 and R 21 are fused ring groups, which may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0138] If R 11 、R 12 、R 13 、R 14 and R 21 are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0139] If R 11 、R 12 、R 13 、R 14 and R 21are alkoxy groups, which may preferably be C1-C 24 Alkoxy group.

[0140] If R 11 、R 12 、R 13 、R 14 and R 21 are aryloxy groups, which may preferably be C6-C 24 Aryloxy group.

[0141] 7) Where L', Ar a and Ar b Same as defined above,

[0142] 8) q, r, s and t are each independently an integer from 0 to 4, u and v are each independently 0 or 1,

[0143] The condition is that except when u and v are both 0, when u or v is 0, Y 3 or Y 4 Does not exist.

[0144] Furthermore, Formula A is represented by Formula 1.

[0145] <Formula 1>

[0146]

[0147] in,

[0148] 1) X is a single bond,

[0149] 2) y is an integer of 0 or 1,

[0150] 3) i) when y is 0, a and b are each independently an integer from 0 to 5,

[0151] ii) when y is 1, a and b are each independently an integer from 0 to 4,

[0152] 4) c and d are each independently an integer from 0 to 4,

[0153] 5)R 1 、R 2 、R 3 and R 4 With R 1' The same definition as

[0154] 6)L 1 , L 2 , L 3 、Ar 1 and Ar 2 Same as defined above, however, L 1 Bonded to any one of * in Formula 1.

[0155] Furthermore, Formula 1 is represented by any one of Formulas 2 to 4.

[0156]

[0157] in

[0158] 1) R 1 、R 2 、R 3 、R 4 ,c,d,L 1 , L 2 , L 3 、Ar 1 and Ar 2 Same as defined above,

[0159] 2) k and l are each independently an integer of 0 to 5, m and n are each independently 0 to 4, and o and p are each independently 0 to 3.

[0160] In addition, Formula 1 is expressed by Formula 5 or Formula 6.

[0161]

[0162] Each of these symbols can be defined as follows.

[0163] 1) R 1 、R 2 、R 3 、R 4 , a, b, c, d, L 1 , L 2 , L 3 、Ar 2 , X and y are the same as defined above,

[0164] 2) R 5 、R 6 and R 7 With R 1' The same definition as

[0165] 3) e is an integer from 0 to 5, f is an integer from 0 to 3, g is an integer from 0 to 4,

[0166] 4)Y 1 is O, S, CR'R" or NR',

[0167] 5) wherein R' and R" are each independently selected from C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; and C3-C 60 Aliphatic ring and C6-C 60Aromatic ring fused ring group; and -L"-N(Ar a )(Ar b ); or R' and R" are bonded to each other to form a C6-C 60 Aromatic ring; Fluorenyl group; C2-C containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring; or C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group;

[0168] Wherein if R' and R" are aryl groups, they may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0169] Wherein if R' and R" are heterocyclic groups, they may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0170] Wherein if R' and R" are fused ring groups, they may preferably be C3-C 30 Aliphatic ring and C6-C 30 Aromatic ring fused ring group, more preferably C3-C 24 Aliphatic ring and C6-C 24 Aromatic ring fused ring group.

[0171] 6) Where L', Ar a and Ar b Same as defined above.

[0172] Equation 1 is expressed by any one of Equations 7 to 15

[0173]

[0174]

[0175] Each symbol can be defined as follows.

[0176] 1)L 1 , L 2 , L 3 , c, d, e, f, g, k, l, m, n, o, p, and Y1 Same as defined above,

[0177] 2) R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 With R 1' The same definition as

[0178] 3) h is an integer from 0 to 5, i is an integer from 0 to 3, j is an integer from 0 to 4,

[0179] 4)Y 2 O, S or CR x R y ,

[0180] 5) Where R x and R y Each independently selected from C1-C 50 Alkyl group; C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 heterocyclic group; or R x and R y bonded to each other to form C6-C 60 Aromatic ring; Fluorenyl group; C2-C containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring; or C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group;

[0181] If R x and R y are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0182] If R x and R y are aryl groups, which may preferably be C6-C 30 Aryl groups, more preferably C6-C 25 Aryl groups, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

[0183] If R x and Ry are heterocyclic groups, which may preferably be C2-C 30 Heterocyclic group, and more preferably C2-C 24 Heterocyclic groups, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, benzothiazine, phenylbenzothiazine, and the like.

[0184] Furthermore, Formula A is represented by any one of the following Compound P-1 to Compound P-20 and Compound P-83 to Compound P-130.

[0185]

[0186]

[0187]

[0188]

[0189] Furthermore, the present invention provides a method for preparing a deuterated compound represented by formula A, comprising:

[0190] (a) a step of forming a first reactant by dissolving a compound represented by formula A in deuterated benzene (benzene-D6);

[0191] (b) a step of forming a second reactant by adding deuterium-trifluoromethanesulfonic acid (CF3SO3D) to the first reactant;

[0192] (c) deuterating the second reactant by reacting it at 80° C. for 3 to 18 hours;

[0193] (d) after the reaction is completed, the second reactant is cooled to room temperature and quenched by adding a D2O solution of Na2CO3,

[0194] (e) After concentrating the organic solvent of the second reactant, the deuterated compound represented by Formula A is obtained by recrystallization using toluene and acetone solvents.

[0195] In step (c), the deuteration reaction time may be 3 hours to 18 hours, and is preferably performed for 3 hours.

[0196] Furthermore, the present invention provides a method for preparing a deuterated compound represented by formula A, wherein the compound represented by formula A is synthesized by reacting a compound represented by formula R1 or formula R2 with a compound represented by formula R3.

[0197]

[0198] Each symbol can be defined as follows.

[0199] 1)L 1 , L 2 , L 3 、Ar 1 、Ar 2 、R 11 、R 12 、R 13 、R 14 , Ring A, Ring B, q, r, s, t, u and v are the same as defined above,

[0200] 2) R 101 and R 102 Each independently selected from C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy groups; and C6-C 30 an aryloxy group; or R 101 and R 102 Bonded to an adjacent group to form a ring.

[0201] If R 101 and R 102 are alkyl groups, which may preferably be C1-C 30 Alkyl groups, more preferably C1-C 24 Alkyl group.

[0202] If R 101 and R 102 are alkoxy groups, which may preferably be C1-C 24 Alkoxy group.

[0203] If R 101 and R 102 are aryloxy groups, which may preferably be C6-C 24 Aryloxy group.

[0204] 3) Z is halogen; or a triflate group;

[0205] 4)w is 0 or 1.

[0206] refer to Figure 1The organic electrical element (100) according to the present invention includes a first electrode (110), a second electrode (170), and an organic material layer containing a single compound or two or more compounds represented by Formula A between the first electrode (110) and the second electrode (170). In this case, the first electrode (110) may be an anode, and the second electrode (170) may be a cathode. In the case of an inverted type, the first electrode may be a cathode, and the second electrode may be an anode.

[0207] The organic material layer may include a hole injection layer (120), a hole transport layer (130), a light emitting layer (140), an electron transport layer (150) and an electron injection layer (160) in sequence on the first electrode (110). In this case, the remaining layers except the light emitting layer (140) may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer (220), a buffer layer (210), etc. may also be included, and the electron transport layer (150) etc. may be used as a hole blocking layer. (See Figure 2 )

[0208] In addition, the organic electrical element according to the embodiment of the present invention may further include a protective layer or a light efficiency enhancement layer (180). The light efficiency enhancement layer may be formed on one of the two surfaces of the first electrode that is not in contact with the organic material layer, or on one of the two surfaces of the second electrode that is not in contact with the organic material layer. The compound according to the embodiment of the present invention suitable for the organic material layer may be used as a host or dopant of a hole injection layer (120), a hole transport layer (130), a luminescent auxiliary layer (220), an electron transport auxiliary layer, an electron transport layer (150) and an electron injection layer (160), a light emitting layer (140), or a material for a light efficiency enhancement layer. Preferably, for example, the compound according to formula A of the present invention may be used as a material for a luminescent auxiliary layer or a hole transport layer.

[0209] The organic material layer may include two or more stacks, including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode, and a charge generation layer formed between the two or more stacks (see Figure 3 ).

[0210] In addition, even in the case of the same core, the band gap, electrical properties, interface properties, etc. may vary depending on the position of the substituent bonding. Therefore, the selection of the combination of the core and the substituent bonded thereto is also very important, and in particular, when the optimal combination of the energy level and T1 value of each organic material layer and the unique properties of the material (mobility, interface properties, etc.) is achieved, long service life and high efficiency can be achieved at the same time.

[0211] The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a PVD (physical vapor deposition) method. For example, a conductive metal or metal oxide or an alloy thereof is deposited on a substrate to form an anode, and an organic material layer including a hole injection layer (120), a hole transport layer (130), a light-emitting layer (140), an electron transport layer (150) and an electron injection layer (160) is formed thereon, and then a material that can be used as a cathode is deposited thereon.

[0212] Furthermore, 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 slit coating process, a dip coating process, and a roll-to-roll process, and the organic material layer provides an organic electrical element containing the compound as an electron transport material.

[0213] As another specific example, the same or different types of compounds represented by Formula A are mixed and used for the organic material layer.

[0214] Furthermore, the present invention provides a light-emitting assisting layer composition including the compound represented by Formula A, and provides an organic electric element including the light-emitting assisting layer.

[0215] Furthermore, the present invention provides a hole transport layer composition including the compound represented by Formula A, and provides an organic electric element including the hole transport layer.

[0216] Furthermore, the present invention provides an electronic device including a display device including an organic electric element; and a control unit for driving the display device.

[0217] On the other hand, the organic electrical element is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a device for monochrome or white lighting. In this case, the electronic device may be a current or future wired / wireless communication terminal and covers all types of electronic devices, including mobile communication terminals such as mobile phones, personal digital assistants (PDAs), electronic dictionaries, point-to-multipoint (PMPs), remote controls, navigation units, game consoles, various TVs, and various computers.

[0218] Hereinafter, Synthesis Examples of the compound represented by Formula A of the present invention and Production Examples of the organic electric element of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[0219] [Synthesis example 1]

[0220] The compound represented by Formula 1 according to the present invention (final product 1-1) can be prepared by reacting Sub 1 with Sub 2 as shown in Scheme 1.

[0221] <Reaction Scheme 1>

[0222]

[0223] The deuterated compound (final product 1-1) of the compound represented by Formula 1 according to the present invention is prepared by dissolving in perdeuterated benzene (benzene-D6), adding deuterium-trifluoromethanesulfonic acid (CF3SO3D), and reacting at a temperature of 80°C for 3 hours to 18 hours, and more preferably 3 hours.

[0224] 1. Synthesis Example of P-1

[0225]

[0226] (1) Synthesis of P1-1

[0227] Sub 1-1 (7.8 g, 22.2 mmol), Sub 2-1 (7.5 g, 22.2 mmol), Pd2(dba)3 (0.6 g, 0.7 mmol), t-BuONa (4.3 g, 44.5 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (130 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.54 mL, 1.3 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 10.8 g (yield: 75%) of P1-1.

[0228] (2) Synthesis of P-1

[0229] The P1-1 (10.8 g, 16.6 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (126.0 g, 1,495.9 mmol), and CF3SO3D (12.5 g, 83.1 mmol) was added thereto, followed by reaction at a temperature of 80°C for 3 hours to form a deuterated substance. Samples were taken regularly, the degree of deuteration was measured by LC-MS, and after the deuterium exchange reaction was completed with the desired substitution rate, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization was performed using toluene and acetone solvents to obtain 10.3 g (yield: 92%) of the deuterated compound P-1. The final mass was determined by LC-MS to confirm that it was 87.1% deuterated.

[0230] 2. Synthesis Example of P-2

[0231]

[0232] (1) Synthesis of P1-2

[0233] Sub 1-2 (9.0 g, 25.5 mmol), Sub 2-2 (8.9 g, 25.5 mmol), Pd2(dba)3 (0.7 g, 0.8 mmol), t-BuONa (4.9 g, 51.0 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (150 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.62 mL, 1.5 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 13.6 g (yield: 80%) of P1-2.

[0234] (2) Synthesis of P-2

[0235] The P1-2 (13.6 g, 20.4 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (154.7 g, 1,838.4 mmol), and CF3SO3D (15.3 g, 102.1 mmol) was added thereto, followed by reaction at a temperature of 80°C for 3 hours to form a deuterated substance. Samples were taken regularly, the degree of deuteration was measured by LC-MS, and after the deuterium exchange reaction was completed with the desired substitution rate, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization using toluene and acetone solvents gave 13.3 g (yield: 94%) of the deuterated compound P-2. Final mass was determined by LC-MS to confirm that it was 87.1% deuterated.

[0236] 3. Synthesis Example of P-3

[0237]

[0238] (1) Synthesis of P1-3

[0239] Sub 1-2 (7.8 g, 22.1 mmol), Sub 2-1 (7.4 g, 22.1 mmol), Pd2(dba)3 (0.6 g, 0.7 mmol), t-BuONa (4.3 g, 44.2 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (130 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.54 mL, 1.3 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 11.4 g (yield: 79%) of P1-3.

[0240] (2) Synthesis of P-3

[0241] The P1-3 (11.4 g, 17.5 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (132.5 g, 1,574.1 mmol), and CF3SO3D (13.1 g, 87.5 mmol) was added thereto, followed by reaction at a temperature of 80°C for 3 hours to form a deuterated substance. Samples were taken regularly, the degree of deuteration was measured by LC-MS, and after the deuterium exchange reaction was completed with the desired substitution rate, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization was performed using toluene and acetone solvents to obtain 10.7 g (yield: 90%) of the deuterated compound P-3. The final mass was determined by LC-MS to confirm that it was 87.8% deuterated.

[0242] 4. Synthesis Example of P-4

[0243]

[0244] (1) Synthesis of P1-4

[0245] Sub 1-4 (9.6 g, 27.2 mmol), Sub 2-4 (10.1 g, 27.2 mmol), Pd2(dba)3 (0.8 g, 0.8 mmol), t-BuONa (5.2 g, 54.4 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (180 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.66 mL, 1.6 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 15.1 g (yield: 81%) of P1-4.

[0246] (2) Synthesis of P-4

[0247] The P1-4 (15.1 g, 22.1 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (167 g, 1,988.7 mmol), and CF3SO3D (16.6 g, 110.5 mmol) was added thereto, followed by reaction at a temperature of 80°C for 3 hours to form a deuterated substance. Samples were taken regularly, the deuterated degree was measured by LC-MS, and after the deuterium exchange reaction was completed with the desired substitution rate, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization was performed using toluene and acetone solvents to obtain 13.8 g (yield: 87%) of the deuterated compound P-4. Final mass was determined by LC-MS to confirm that it was 83.7% deuterated.

[0248] [Synthesis example 2]

[0249] The compound represented by Formula A according to the present invention (final product 2) is prepared by a reaction according to Reaction Scheme 2.

[0250] <Reaction Scheme 2>

[0251]

[0252] The deuterated compound (final product 2) of the compound represented by formula A according to the present invention is prepared by dissolving in perdeuterated benzene (benzene-D6), adding deuterium-trifluoromethanesulfonic acid (CF3SO3D), and reacting at a temperature of 80°C for 3 hours to 18 hours, more preferably 3 hours to 18 hours, more preferably 3 hours.

[0253] 1. Synthesis Example of P-84

[0254]

[0255] (1) Synthesis of P1-84

[0256] Sub 1-84 (10.0 g, 23.7 mmol), Sub 2-84 (4.3 g, 23.7 mmol), Pd2(dba)3 (0.7 g, 0.7 mmol), t-BuONa (4.6 g, 47.4 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (119 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.6 mL, 1.4 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 10.0 g (yield: 78%) of P1-84.

[0257] (2) Synthesis of P-84

[0258] P1-84 (10.0 g, 18.5 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (132 g, 1,568.7 mmol), and CF3SO3D (13.1 g, 87.2 mmol) was added thereto, followed by reaction at a temperature of 80°C.

[0259] 3 hours regular sampling, and by LC-MS measurement deuterated degree, after the deuterium exchange reaction is completed with the desired substitution rate, cooled to room temperature, quenched by adding Na2CO3 D2O solution, and concentrated organic solvent. Recrystallization using toluene and acetone solvents gave 9.7 g (yield: 93%) of deuterated compound P-72. Final mass was determined by LC-MS to confirm that it was 80.6% deuterated.

[0260] 2. Synthesis Example of P-106

[0261]

[0262] (1) Synthesis of P1-106

[0263] Sub 1-106 (10.0 g, 20.8 mmol), Sub 2-106 (3.8 g, 20.8 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), t-BuONa (4.0 g, 41.5 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (104 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.5 mL, 1.3 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 10.1 g (yield: 77%) of P1-106.

[0264] (2) Synthesis of P-106

[0265] P1-106 (10.1 g, 16 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (120.7 g, 1,434.2 mmol), and CF3SO3D (12.0 g, 79.7 mmol) was added thereto, followed by reaction at a temperature of 80°C.

[0266] 3 hours regular sampling, and by LC-MS measurement of deuterated degree, after the deuterium exchange reaction is completed with the desired substitution rate, cooled to room temperature, quenched by adding Na2CO3 D2O solution, and concentrated organic solvent. Recrystallization using toluene and acetone solvents gave 9.8 g (yield: 94%) of deuterated compound P-106. Final mass was determined by LC-MS to confirm that it was 74.3% deuterated.

[0267] 3. Synthesis Example of P-119

[0268]

[0269] (1) Synthesis of P1-119

[0270] Sub 1-119 (10.0 g, 19.0 mmol), Sub 2-119 (3.5 g, 19.0 mmol), Pd2(dba)3 (0.5 g, 0.6 mmol), t-BuONa (3.6 g, 38.0 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (95 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (0.5 mL, 1.1 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2=4:1) to obtain 10.1 g (yield: 78%) of P1-119.

[0271] (2) Synthesis of P-119

[0272] P1-119 (10.1 g, 14.8 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (112.7 g, 1,339.0 mmol), and CF3SO3D (11.2 g, 74.4 mmol) was added thereto, followed by reaction at a temperature of 80°C.

[0273] 3 hours regular sampling, and by LC-MS measurement of deuterated degree, after the deuterium exchange reaction is completed with the desired substitution rate, cooled to room temperature, quenched by adding Na2CO3 D2O solution, and concentrated organic solvent. Recrystallization using toluene and acetone solvents gave 9.8 g (yield: 93%) of deuterated compound P-119. Final mass was determined by LC-MS to confirm that it was 84.2% deuterated.

[0274] 4. Synthesis Example of P-124

[0275]

[0276] (1) Synthesis of P1-124

[0277] Sub 1-124 (10.0 g, 30.7 mmol), Sub 2-119 (5.8 g, 30.7 mmol), Pd2(dba)3 (0.8 g, 0.9 mmol), t-BuONa (5.9 g, 1.8 mmol) were placed in a round-bottom flask and dissolved in anhydrous toluene (154 mL), followed by the addition of P(t-Bu)3 (50 wt% solution) (2.1 mL, 1.8 mmol), heated and stirred at 110°C for about 4 hours. After the reaction was confirmed to be complete by TLC, it was cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column (hexane: CH2Cl2 = 4:1) to obtain 15.7 g (yield: 72.4%) of P1-124.

[0278] (2) Synthesis of P-124

[0279] P1-124 (15.7 g, 22.2 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (168.4 g, 2,001.6 mmol), and CF3SO3D (16.7 g, 111.2 mmol) was added thereto, followed by reaction at a temperature of 80°C.

[0280] 3 hours regular sampling, and by LC-MS measurement of deuterated degree, after the deuterium exchange reaction is completed with the desired substitution rate, cooled to room temperature, quenched by adding Na2CO3 D2O solution, and concentrated organic solvent. Recrystallization using toluene and acetone solvents gave 15.2 g (yield: 93%) of deuterated compound P-124. Final mass was determined by LC-MS to confirm that it was 82.8% deuterated.

[0281] [Comparative Synthesis Example 1]

[0282]

[0283] [Synthesis of Comparative Compound A-1]

[0284] The P1-1 (10.0 g, 15.4 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (116.5 g, 1,385.1 mmol), and CF3SO3D (11.6 g, 77.0 mmol) was added thereto, followed by reaction at a temperature of 50°C for 20 hours to form a deuterated substance. After the reaction was complete, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization using toluene and acetone solvents gave 9.2 g (yield: 91%) of deuterated compound A-1. Final mass was determined by LC-MS to confirm that it was 22.6% deuterated.

[0285] [Comparative Synthesis Example 2]

[0286]

[0287] [Synthesis of Comparative Compound A-2]

[0288] The P1-84 (9.0 g, 15.7 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (118.8 g, 1,411.8 mmol), and CF3SO3D (11.8 g, 78.4 mmol) was added thereto, followed by reaction at a temperature of 50°C for 20 hours to form a deuterated substance. After the reaction was complete, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization using toluene and acetone solvents gave 8.5 g (yield: 94%) of deuterated compound A-2. Final mass was determined by LC-MS to confirm that it was 22.6% deuterated.

[0289] [Comparative Synthesis Example 3]

[0290]

[0291] [Synthesis of Comparative Compound A-3]

[0292] The P1-119 (10.0 g, 14.7 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (111.6 g, 1,325.7 mmol), and CF3SO3D (11.1 g, 73.7 mmol) was added thereto, followed by reaction at a temperature of 50°C for 20 hours to form a deuterated substance. After the reaction was complete, it was cooled to room temperature, quenched by adding a D2O solution of Na2CO3, and the organic solvent was concentrated. Recrystallization using toluene and acetone solvents gave 9.4 g (yield: 93%) of deuterated compound A-3. Final mass was determined by LC-MS to confirm that it was 21.1% deuterated.

[0293] From the results of Comparative Synthesis Examples 1 to 3, it can be seen that, compared with the preparation method of the present invention, conventionally known general deuterium substitution methods have long reaction times and are difficult to control at a significantly lower deuterium substitution rate. In the preparation method described in the present invention, the reaction time can be reduced by reacting at an elevated temperature for a period of time, preferably 3 hours, compared to the existing reaction temperature, and a deuterated compound with an improved substitution rate can be obtained.

[0294] Meanwhile, the FD-MS (field desorption-mass spectrometry) values of the compounds of the present invention prepared according to the above synthesis examples are shown in Table 1.

[0295] [Table 1]

[0296]

[0297] Manufacturing and evaluation of organic electrical components

[0298] [Example 1] Blue organic light-emitting device (light-emitting auxiliary layer)

[0299] After 2-TNATA is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to a thickness of 60 nm to form a hole injection layer, NPB is vacuum-deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Then, compound P-1 of the present invention is vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a luminescence auxiliary layer, and then 9,10-di(naphthalene-2-yl)anthracene as a host and BD-052X (manufactured by Idemitsu Kosan) as a dopant are used on the luminescence auxiliary layer in a weight ratio of 96:4 to form a light-emitting layer with a thickness of 30 nm. Subsequently, (1,1'-biphenyl-4-ato)bis(2-methyl-8-hydroxyquinolinolato)aluminum (hereinafter, BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole-blocking layer. Bis(10-hydroxybenzo[h]quinolinolato)beryllium (hereinafter, BeBq2) was then vacuum-deposited to a thickness of 40 nm on the hole-blocking layer to form an electron-transporting layer. LiF, an alkali metal halide, was then deposited to a thickness of 0.2 nm to form an electron-injection layer, and Al was then deposited to a thickness of 150 nm to form a cathode, thereby fabricating an organic electroluminescent device.

[0300] [Example 2] to [Example 20] Blue organic electroluminescent device (luminescence auxiliary layer)

[0301] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds of the present invention described in Table 2 were used instead of the compound P-1 of the present invention as the light-emitting auxiliary layer material.

[0302] [Comparative Example 1] to [Comparative Example 6]

[0303] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compounds 1 to 6 described in Table 2 were used as the light-emitting auxiliary layer material instead of Compound P-1 of the present invention.

[0304]

[0305]

[0306] Electroluminescence (EL) characteristics were measured by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 20 and Comparative Examples 1 to 6 of the present invention using a PR-650 from Photoresearch, and a lifetime measurement device manufactured by McScience at 500 cd / m 2 The T95 service life was measured under standard brightness, and the measurement results are shown in Table 2.

[0307] [Table 2]

[0308]

[0309]

[0310] As can be seen from the results in Table 2, when the material for an organic electroluminescent device of the present invention is used as a light-emitting auxiliary layer material to manufacture a blue organic light-emitting device, the service life of the organic electroluminescent device can be significantly improved compared to the comparative examples using Comparative Compounds 1 to 6. In detail, compared to Comparative Compounds 1, 3, and 5, which are not substituted with deuterium, Comparative Compounds 2, 4, and 6, which are partially substituted with deuterium, showed improved device results with improved driving voltage, efficiency, and service life, and compared to Comparative Compounds 2, 4, and 6, the compounds of the present invention, in which 74% or more of the total hydrogen is substituted with deuterium, showed excellent device results in terms of service life.

[0311] When deuterium is substituted, the deuterium-carbon bond length becomes shorter than the hydrogen-carbon bond length, which reduces the molecular core volume and thus reduces the electric polarizability. This can reduce the crystallinity of the film, i.e., the amorphous state, and thus increase the hole mobility.

[0312] It can be seen that, in particular, the compounds of the present invention are deuterated at a substitution rate of 74% to 98% (which is higher than the existing substitution rate), which increases the BDE (bond dissociation energy) compared to the comparative compound, thereby maximizing the bond stability of the structure, and thus, improving the stability of the molecules in the device, so that the results in terms of service life are significantly excellent.

[0313] This suggests that even if they have similar structures, physical properties, and properties of compounds, the results of the devices can differ significantly depending on the deuterium substitution rate.

[0314] In the case of the luminescent auxiliary layer, it is necessary to understand the correlation between the hole transport layer and the luminescent layer (host), and even if a similar core is used, it is difficult for a technician in this field to infer the characteristics exhibited by the luminescent auxiliary layer in which the compound of the present invention is used.

[0315] In the evaluation results of the above device fabrication, device characteristics have been described in which the compound of the present invention is applied only to the hole transport layer, but the compound of the present invention can also be applied to the hole transport layer, or to both the hole transport layer and the light-emitting assisting layer.

[0316] Although the exemplary embodiments of the present invention have been described for illustrative purposes, it will be understood by those skilled in the art that various modifications, additions, and substitutions are possible without departing from the scope and spirit of the invention as disclosed in the appended claims. Therefore, the embodiments disclosed in the present invention are intended to illustrate the scope of the technical concept of the present invention, and the scope of the present invention is not limited by the embodiments. The scope of the present invention should be interpreted based on the appended claims, and should be interpreted as including all technical concepts within the scope equivalent to the claims belonging to the present invention.

[0317] [Industrial Applicability]

[0318] According to the present invention, an organic device having excellent device characteristics of high luminance, high luminescence, and long life can be manufactured, and thus has industrial applicability.

Claims

1. A compound represented by formula A which is 74% to 98% deuterated: Formula A in: 1)L 1 , L 2 and L 3 Each independently selected from a single bond; C6-C 60 Arylene group; Fluorenylene group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; and C2-C 60 heterocyclic groups; 2)Ar 1 and Ar 2 Each independently selected from C6-C 60 Aryl group; and C2-C containing at least one heteroatom of O, N, S, Si or P 60 heterocyclic groups; 3)Ar 3 Represented by the formula Ar-1 * means L bonded to formula A 1 location; 4)X 1 is O or S; 5) Ring A is selected from C6-C 60 Aryl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; and C3-C 60 Aliphatic ring and C6-C 60 A fused aromatic ring group; or ring A may be R 21 replace; 6)R 11 and R 21 are each independently selected from hydrogen; deuterium; halogen; cyano group; C6-C 60 Aryl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 an aryloxy group; or R 11 and R 21 bonded to adjacent groups to form a ring; 7) wherein the aryl group, the arylene group, the heterocyclic group, the fluorenyl group, the fluorenylene group, the condensed ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group and the aryloxy group may be substituted by one or more substituents selected from deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1-C 20 Alkylthio group; C1-C 20 Alkoxy group; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C6-C 20 Aryl group; deuterium-substituted C6-C 20 Aryl group; Fluorenyl group; C2-C 20 Heterocyclic group; C3-C 20 Cycloalkyl group; C7-C 20 Arylalkyl group; and C8-C 20 Arylalkenyl group; In addition, the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term "ring" means C3-C 60 Aliphatic ring or C6-C 60 Aromatic ring or C2-C 60 a heterocyclic group or a condensed ring formed by combining them.

2. A compound represented by any one of the following compounds P-99 to P-130:

3. A method for preparing the deuterated compound represented by formula A according to claim 1, comprising: (a) a step of forming a first reactant by dissolving the compound represented by formula A in deuterated benzene (benzene-D6); (b) a step of forming a second reactant by adding deuterium-trifluoromethanesulfonic acid (CF3SO3D) to the first reactant; (c) deuterating the second reactant by reacting it at 80° C. for 3 to 18 hours; (d) after the reaction is completed, cooling the second reactant to room temperature and quenching the reaction by adding a Na2CO3 D2O solution; (e) After concentrating the organic solvent of the second reactant, recrystallizing the reactant using toluene and acetone solvents to obtain the deuterated compound represented by formula A.

4. A method for preparing a deuterated compound represented by formula A according to claim 1, wherein the compound represented by formula A is synthesized by reacting a compound represented by formula R1 with a compound represented by formula R3: in: 1)L 1 , L 2 , L 3 、Ar 1 and Ar 2 Same as defined in claim 1, 2) R 11 , Ring A and q are the same as defined in claim 1, 3) R 101 and R 102 Each independently selected from C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy groups; and C6-C 30 an aryloxy group; or R 101 and R 102 bonded to an adjacent group to form a ring, 4) Z is halogen; or a triflate group; 5)w is 0 or 1. 5 . An organic electrical element comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode, wherein the organic material layer comprises one or more of the compounds according to claim 1 . 6 . The organic electrical element according to claim 5 , wherein the organic material layer comprises at least one of a hole injection layer, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. 7 . The organic electric element according to claim 5 , wherein the organic material layer is a light-emitting auxiliary layer.

8. The organic electric element according to claim 5, wherein the organic material layer is a hole transport layer. 9 . The organic electric element according to claim 5 , wherein the organic electric element further comprises a light efficiency enhancing layer formed on at least one surface of the anode and the cathode, the surface being opposite to the organic material layer. 10 . The organic electric element according to claim 5 , wherein the organic material layer comprises two or more stacked bodies, the stacked bodies comprising a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode. 11 . The organic electric element according to claim 10 , wherein the organic material layer further comprises a charge generation layer formed between the two or more stacked bodies.

12. An electronic device comprising a display device including the organic electric element according to claim 5; and a control unit for driving the display device. 13 . The electronic device according to claim 12 , wherein the organic electric element is at least one of an OLED, an organic solar cell, an organic photoconductor, an organic transistor, and an element for monochromatic or white lighting.

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