KR102040745B1 - Novel compound and organic electronic device comprising the same - Google Patents

Abstract

Ar₁, Ar₂, Ar₃, Ar₄, L, Q, G, n1, n2, m1, m2 및 q는 명세서에서 정의한 바와 동일하다. 또한, 본 발명의 상기 신규 화합물을 포함하는 유기 전자 소자를 개시한다.The present invention discloses a novel compound represented by the following Formula (I),

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , L, Q, G, n1, n2, m1, m2 and q are the same as defined in the specification. Also disclosed is an organic electronic device comprising the novel compound of the present invention.

Description

Novel compound and organic electronic device including the same {NOVEL COMPOUND AND ORGANIC ELECTRONIC DEVICE COMPRISING THE SAME}

The present invention relates to novel compounds and organic electronic devices using the same.

Organic light emitting devices (OLEDs) were first invented and proposed by Eastman Kodak through a vacuum evaporation method. Tang and VanSlyke from Kodak Company deposited electron transport materials, such as Alq3, on transparent indium tin oxide (ITO) glass with an organic layer of aromatic diamine. A metal electrode was vapor-deposited on the Alq3 layer, and then fabrication of the organic electroluminescent (EL) device was completed. Organic EL devices are the next generation of lighting devices due to high brightness, fast response speed, light weight, compressibility, true color, absence of viewing angles difference, non-use of LCD backlight plate and low power consumption. Or display.

Recently, some intermediate layers, such as electron transport layers and hole transport layers, are added between the cathode and anode to increase the current and power efficiency of the OLED. For example, an organic light emitting diode (OLED) 1 ′ as shown in FIG. 1 includes a cathode 11 ′, an electron injection layer 13 ′, and a light emitting layer 14 ′. ), A hole transport layer 16 'and an anode 18'.

Recently, in order to effectively improve the lighting performance of OLEDs, OLED manufacturers and researchers have made great efforts to develop various compounds used as OLED materials. However, despite the development of various compounds, current phosphorescent OLEDs are still not excellent in luminous efficiency and device life. Accordingly, in view of conventional or commercially used OLED materials that still contain disadvantages, the present inventors have made a lot of efforts to study the present invention and have provided novel compounds for OLEDs.

It is an object of the present invention to provide a novel compound and an organic electronic device comprising the same.

In one or more examples, the compound is represented by formula (I):

Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₆ -C ₄₀ aryl group (aryl group), a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group, (heterocyclic group), or a substituted or unsubstituted amine group (amine group) and; Or Ar ₁ and Ar ₂ together with the nitrogen atom bonded to them form a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group; Or Ar ₃ and Ar ₄ together with the nitrogen atom bonded to them form a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group;

L and Q are each independently a substituted or unsubstituted C ₆ -C ₄₀ arylene group (arylene group) and;

G is deuterium, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₄₀ aryl group, a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group, or a substituted or unsubstituted An amine group;

n1 and n2 are each independently 0 or 1;

m1 and m2 are each independently 0,1 or 2, provided that m1 and m2 are not 0 at the same time; And

q is 0, 1 or 2.

In accordance with one or more embodiments, the organic electronic device comprises a first electrode; Second electrode; And an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a compound of formula (I).

The present invention provides novel compounds. When the compound of the present invention is used in an organic electronic device, the efficiency of the organic electronic device can be improved. In particular, when using the novel compound of the present invention as a material of the organic light emitting device, it is possible to further improve the luminous efficiency of the organic light emitting device.

1 is a perspective view showing a conventional OLED device.
2 is a perspective view showing an OLED device of the present invention.
3 is a perspective view showing an organic solar cell element of the present invention.
4 to 23 show Compound (1) (SGM178), Compound (2) (SGM179), Compound (3) (SGM180), Compound (4) (SGM181) and Compound (5) (SGM182) of the present invention, respectively. , Compound (6) (SGM271), Compound (8) (SGM410), Compound (9) (SGM436), Compound (10) (SGM437), Compound (11) (SGM438), Compound (12) (SGM439), Compound (13) (SGM273), Compound (15) (SGM116), Compound (16) (SGM175), Compound (17) (SGM176), Compound (18) (SGM177), Compound (19) (SGM542), Compound (21 1H NMR data of (SGM563), Compound 23 (SGM562) and Compound 24 (SGM575) are shown.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. It is to be understood that the description of the invention has been described in an illustrative manner, and that the terminology used is intended to be in the nature of words of description and not of limitation. Many modifications and variations of the present specification are possible. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

compound

The compound according to one embodiment may be represented by the following formula (I).

According to one embodiment, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently a substituted or unsubstituted C ₆ -C ₄₀ aryl group, or a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic Group; Or Ar ₁ and Ar ₂ together with the nitrogen atom bonded to them form a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group; Or Ar ₃ and Ar ₄ may form together with the nitrogen atom bonded to them a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group. Preferably, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently a substituted or unsubstituted C ₆ -C ₄₀ aryl group, or a substituted or unsubstituted C ₁ -C ₄₀ heteroaryl group (heteroaryl group); Or Ar ₁ and Ar ₂ may form a substituted or unsubstituted C ₁ -C ₄₀ heteroaryl group together with the nitrogen atom linking them; Or Ar ₃ and Ar together with the nitrogen atom bonded to them form a substituted or unsubstituted C ₁ -C ₄₀ heteroaryl group.

According to one embodiment, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ Are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group group, substituted or unsubstituted tribenzyloxepinyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiofuranyl group, substituted or unsubstituted It may be a substituted naphthyl group, or a substituted or unsubstituted tribenzyl-azepinyl group. Preferably, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently unsubstituted phenyl, alkyl substituted phenyl, unsubstituted biphenyl, unsubstituted terphenyl, unsubstituted fluorenyl , Alkyl substituted fluorenyl, unsubstituted tribenzyloxepinyl, unsubstituted dibenzofuranyl, or unsubstituted naphthyl.

According to one embodiment, m1 may be 1; m2 may be 0 or 1. According to another embodiment, m1 may be 1 and m2 may be 0. According to yet another embodiment, m1 may be 1 and m2 may be 1.

According to one embodiment, m1 may be 1; m2 can be 0; Ar ₁ and Ar ₂ may form together with the nitrogen atom bonded to them a substituted or unsubstituted C ₁ -C ₄₀ heteroaryl group. Preferably, Ar ₁ and Ar ₂ together with the nitrogen atom bonded thereto form an unsubstituted tribenzyl-azinyl group.

According to an embodiment, when m1 and m2 are not 0 at the same time, -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ may be the same.

According to one embodiment, m1 and m2 are 1, and -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ may be the same.

According to an embodiment, L and Q may each independently be substituted or unsubstituted phenylene, biphenylene, or naphthylene. Preferably, L and Q are each independently an unsubstituted phenylene group.

According to one embodiment, q may be 0 or 1.

When q is 1, G may be a substituted or unsubstituted C ₆ -C ₄₀ aryl group, a substituted or unsubstituted C ₁ -C ₄₀ heterocyclic group. Preferably, G is a substituted or unsubstituted C ₆ -C ₄₀ aryl group or a substituted or unsubstituted C ₁ -C ₄₀ heteroaryl group comprising a nitrogen atom. More preferably, G is substituted or unsubstituted phenyl or unsubstituted pyridyl.

According to one embodiment, G, -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ may be the same or different. For example, when m1 is 1, m2 is 1 and q is 1, -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ may be the same, and G and -L _n1 -NAr ₁ Ar ₂ , -Q _n2 -NAr ₃ Ar ₄ is different.

According to one embodiment, the compound of formula (I) may be represented by any one of the following formula (I-1) to (I-6).

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , L, Q, G, n1 and n2 of formulas (I-1) to (I-6) are as described above.

According to one embodiment, -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ are each independently selected from the group consisting of the following compounds:

In the above formula, * represents a bonding position, Ra and Rb are each independently C _1-20 alkyl, and x and y are each independently 1 or 2. Here, Ra and Rb may be the same. x and y may be the same. Examples of Ra and Rb may be methyl, ethyl or propyl. Also, n1 or n2 may be zero.

According to one embodiment, n1 is 0 and n2 is 1. According to another embodiment, n1 is 1 and n2 is 1. In these two examples, -L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ Are each independently selected from the group consisting of:

In the formula, * represents the bonding positions. The definitions of Ra, Rb, x and y are as described above. In these two embodiments, L and Q (e.g. phenylene (phenylene)) each independently represent a substituted or unsubstituted C ₆ -C ₄₀ arylene group may be a.

Hereinafter, the substituent of Formula (I) is demonstrated in detail. Substituents not defined in the present invention are defined as known in the art.

In this specification, the unsubstituted alkyl group may be linear or branched. Examples of the alkyl group, includes a C _{1 -20} alkyl, C _1-10 alkyl, or C _{1- 6} alkyl. Specific examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso- Butyl (iso-butyl), tert-butyl, tert-butyl, pentyl, neo-pentyl, or hexyl. Here, at least one hydrogen of the unsubstituted alkyl group is a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, an aryl group, an arylalkyl group group), an arylalkenyl group, a heterocyclic group, a nitrile group, or an acetylene group.

In this specification, an unsubstituted aryl group means an aromatic hydrocarbon group. Examples of the aryl group may be a C ₆ -C ₄₀ aryl group or a C ₆ -C ₂₀ aryl group. In addition, examples of the aryl group may be a monocyclic, bicyclic, tricyclic or polycyclic aromatic hydrocarbon group; Two or more rings may be fused to each other or linked to each other through a single bond. Specific examples of the unsubstituted aryl group include phenyl, biphenylyl, terphenyl, quarterphenyl, naphthyl, anthryl, benzanthryl , Phenanthryl, naphthacenyl, pyrenyl, chrysenyl, benzo [c] phenanthryl, benzo [g] crissenyl (benzo [g] chrysenyl, triphenylenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, or dibenzofluorenyl groups, including but not limited to . Here, one or more hydrogen atoms of the unsubstituted aryl group may be substituted with the same substituent as described above in connection with the alkyl group. In addition, the definition of the arylene group is similar to those described above, and the detailed description of the arylene group is not repeated herein.

In this specification, an unsubstituted heterocyclic group means a non-aromatic or aromatic hydrocarbon group. Examples of the heterocyclic group are, can be a C ₁ -C ₄₀ heterocyclic group, C ₂ -C ₂₀ heterocyclic group, or C ₄ -C ₂₀ heterocyclic. In addition, examples of the heterocyclic group include polycyclic heteroaryl having at least one heteroatom selected from the group consisting of monocyclic, bicyclic, tricyclic, or O, S and N. Or a heterocycloalkyl group; Two or more rings may be fused to each other or linked to each other through a single bond. The unsubstituted heterocyclic group is pyroryl, pyrazinyl, pyridinyl, pyridinyl, piperidinyl, indolyl, isoindoleyl, imidazolyl ( imidazolyl, benzoimidazolyl, furyl, ozazolyl, thiazolyl, triazolyl, thiadiazolyl, benzothiazolyl, benzothiazolyl, tetrazolyl (tetrazolyl), oxadiazolyl, triazinyl, carbazolyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzofuranyl, dibenzothio Furanyl (dibenzothiofuranyl), dibenzothiophenyl (dibenzothiophenyl), quinolyl (quinolyl), isoquinolyl, quinoxalinyl (quinoxalinyl), phenantridinyl, acridinyl, phenanthrolyne Phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxa (phenoxazinyl), oxazolyl, oxadiazoyl, furazanyl, furazanyl, thienyl, benzothiophenyl, tribenzyloxepinyl, thiophenyl , Or benzooxazolyl. Here, one or more hydrogen atoms of the unsubstituted heterocyclic group may be substituted with the same substituent as described above in connection with the alkyl group.

In the present specification, halogen includes F, Cl, Br and I; Preferably F or Br.

In this specification, the unsubstituted alkoxy group refers to a moiety in which the alkyl defined above is bonded to an oxygen atom. Examples of the alkoxy group are linear or branched C _1-10 alkoxy or linear or branched C _1-6 alkoxy group. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, neo-pentyloxy or hexyloxy ( hexyloxy), but is not limited thereto. Here, one or more hydrogen atoms of the unsubstituted alkoxy group may be substituted with the same substituent as described above in connection with the alkyl group.

As used herein, the unsubstituted cycloalkyl group refers to a monovalent saturated hydrocarbon ring system having 3 to 20, or 3 to 12 carbon atoms. Examples of such unsubstituted cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl It is not limited to this.

In this specification, the unsubstituted alkenyl group may be linear or branched, and has one or more carbon-carbon double bonds. Examples of the alkenyl group include C ₁ -C ₂₀ alkenyl, C _1-10 alkenyl, or C _1-6 alkenyl. Specific examples of the unsubstituted alkenyl group include ethenyl, propenyl, propenylene, allyl, or 1,4-butadienyl (1,4-butadienyl) Including but not limited to. Here, one or more hydrogen atoms of the unsubstituted alkenyl group may be substituted with the same substituent as described above in connection with the alkyl group.

Examples of the compounds of formula (I) may include any of compounds (1) to (122).

Here, one or more hydrogen atoms of the compounds (1) to (122) may be optionally substituted with further substituents described above.

Organic electronic devices

The present specification also provides an organic electronic device comprising the compounds.

In one embodiment, the organic electronic device, a first electrode; Second electrode; And an organic layer disposed between the first electrode and the second electrode, wherein the organic layer includes the compounds.

As used herein, the term "organic layer" refers to a single layer or multiple layers disposed between a first electrode and a second electrode of an organic electronic device.

Application products of the organic electronic device of the present disclosure, an organic light emitting device, an organic solar cell device, an organic thin film transistor, an organic photodetector, a flat panel display, a computer monitor (computer monitor), television, billboard, indoor or outdoor lighting illuminator, indoor or outdoor signage illuminator, heads up display, fully transparent display, flexible display, laser printer ( laser printers, telephones, cell phones, tablet computers, laptop computers, digital cameras, camcorders, viewfinders, micro-displays Vehicles, vehicles, large area walls, theater or stadium screens or signs. Preferably, the electronic device of the present specification is applied to an organic light emitting device or an organic solar cell device.

In one embodiment, the organic electronic device may be an organic light emitting device. 2 is a perspective view showing the structure of another organic light emitting device according to an embodiment of the present invention. As shown in FIG. 2, the organic light emitting device includes: a substrate 11; Anode 12; Cathode 18; And an organic layer comprising a hole injection layer 13, a hole transport layer 14, a light emitting layer 15, an electron transport layer 16 and an electron injection layer 17. However, the present specification is not limited thereto. In addition, other layers capable of improving the luminous efficiency of the organic light emitting device, such as an electron blocking layer or a hole blocking layer, may be formed in the organic light emitting device of the present invention. When the organic light emitting device of the present invention further includes the electron blocking layer, the electron blocking layer may be disposed between the hole transport layer 14 and the light emitting layer 15. When the organic light emitting device of the present invention further includes the hole blocking layer, the hole blocking layer may be disposed between the electron transport layer 16 and the light emitting layer 15.

In one embodiment, the organic light emitting device of the present invention, may include a hole transport layer containing the compound. In another embodiment, the organic light emitting diode of the present invention may include a hole injection layer including the compound. In another embodiment, the organic light emitting diode of the present invention may include an electron blocking layer including the compound. However, the present invention is not limited thereto.

In one embodiment, the light emitting layer may include a phosphorescent light emitting material which may include iridium or platinum. In another embodiment, the light emitting layer may include quantum dots or semiconductor nanocrystal material. However, the present invention is not limited thereto.

In another embodiment, the organic electronic device may be an organic solar cell. 3 is a perspective view showing the structure of an organic solar cell according to the present invention. As shown in FIG. 3, the organic solar cell includes: a first electrode 21; Second electrode 22; The organic layer 23 may be disposed between the first electrode 21 and the second electrode 22 to include any one of the compounds. The organic layer 23 may be provided as a carrier transport layer.

Other objects, advantages and novel features of the invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

Example

The following examples are provided to illustrate features of the present invention. However, the present invention is not limited by the following examples.

Unless otherwise indicated, the following synthesis is carried out in a protected-gas atmosphere. Starting materials can be purchased from Aldrich or Alfa or obtained according to literature procedures.

synthesis Example  1- Intermediate A1 to A15 and their synthesis

Intermediates A1 to A15 used to prepare the compounds of formula (I) are listed in Table 1 below, with the number below each intermediate representing its CAS number.

Intermediates A1 to A10, A14 and A15

Intermediates A1 to A10, A14 and A15 were purchased from Aldrich or Alfa and CAS numbers are listed above.

Synthesis of Intermediates A11 to A13

The intermediates A11 to A13 can be prepared according to Scheme I above. Starting materials Ar ₁ -NH ₂ (arylamine) and Br-Ar ₂ (arylbromide) are listed in Table 2 below.

Briefly, arylbromide (1.0eq), arylamine (1.05eq), Pd (OAc) ₂ (0.01eq), 1,1'-bis (diphenylphosphino) ferrocene (1,1'-Bis (diphenylphosphino) ferrocene , DPPF) (0.04eq), sodium tert-butoxide (1.5eq) and toluene were placed in a round bottom flask and heated at 80 ° C. for 12 hours under N ₂ atmosphere. After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL). The mixed organic extracts were washed with brine solution, dried over Na ₂ SO ₄ and concentrated to give a yellow solid. The crude product was also purified by column chromatography on silica gel using a hexane / dichloromethane mixture (2: 1 v / v) as eluent. Analytical data of the obtained product, namely intermediates A11 to A13, are listed in Table 2 below.

synthesis Example 2  Intermediates B1 to B4 and their synthesis

Intermediates B1 to B4 used to prepare the compounds of formula (I) are listed in Table 3 below.

Synthesis of Intermediate B1

The intermediate B1 can be prepared according to the schematic II above.

Step 1  Synthesis of Intermediate B1-1

3-bromodibenzo [a, d] cyclohepten-5-one (86 g, 1.0 eq), N -bro in carbon tetrachloride (430 ml) A mixture of N- Bromosuccinimide (106 g, 2.0 eq), and benzyl peroxide (0.7 g, 0.01 eq) was heated at 85 ° C. The reaction was monitored by HPLC. After completion of the reaction, the precipitate was separated by filtration, washed with MeOH and purified by recrystallization. The purified product was concentrated to dryness to afford 123 g of a white solid product in 92.3% yield. FD-MS analysis C ₁₅ H ₉ Br ₃ O: Theoretical value 444.94, Observation 444.94.

Step 2  : Synthesis of Intermediate B1-2

The obtained B1-1 (116.0 g, 1.0eq) was dissolved in 960 ml of furan / THF (v / v = 2/1), and the reaction was cooled to 0 ° C., followed by KO- t- Bu ( 87.8 g, 3.0 eq). The reaction was stirred at 0 ° C. for 1 h and then raised to room temperature and stirred for a further 12 h. After completion of the reaction, the mixture was quenched with DI water, the organic layer was recovered by a solvent extraction operation, and dried over sodium sulfate. From the organic layer, the solvent was removed by distillation under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The purified product was concentrated to dryness to give 46.8 g of a light yellow solid product in 51.1% yield. FD-MS analysis C ₁₉ H ₁₁ BrO ₂ : Theoretical 351.19, Observed 351.19.

Step 3: Synthesis of Intermediate B1-3

A suspension of the intermediate B1-2 (53.5 g, 1.0 eq) and 5% Pd / C (8.1 g, 0.025 eq) obtained in 535 ml of ethyl acetate was charged with a hydrogen balloon. Stir for 3-6 hours under air. The resulting mixture was filtered through a pad of celite, washed with ethyl acetate and the filtrate was concentrated under reduced pressure to give 100 g (100%) of intermediate B1-3 as a yellow solid. The obtained compound, intermediate B1-3, was used directly in the next reaction without further purification.

Step 4: Synthesis of Intermediate B1

The toluene of the obtained intermediate 530ml B1-3 (53g, 1.0eq) and p - toluene sulfonic acid (p -toluenesulfonic acid) (57g, 2.0eq) was heated to 110 ℃ for 12 hours. The reaction mixture was cooled to room temperature, then quenched with a saturated aqueous solution of NaHCO ₃ and extracted with CH ₂ Cl ₂ . The organic layer was washed with water, brine and then dried over anhydrous Na ₂ SO ₄ (anhydrous Na ₂ SO ₄ ). The resulting solution was then concentrated under reduced pressure and purified by column chromatography on silica gel using CH ₂ Cl ₂ / hexane 1/1 (v / v) as eluent. 46.0 g of intermediate B1 was obtained as a light yellow solid in a yield of 91.5%. FD-MS analysis C ₁₉ H ₁₁ BrO: Theoretical value 335.19, Observation 335.19.

Synthesis of Intermediates B2 and B3

Synthesis of intermediates B2 and B3 was carried out in the same manner as in the preparation of intermediate B1, except that 3-bromodibenzo [a, d] cyclohepten-5-one used in the preparation of intermediate B1 was used as intermediate B2. Was replaced with 2-bromodibenzo [a, d] cyclohepten-5-one to prepare 3,7-di to prepare intermediate B3. Bromobenzo [a, d] cyclohepten-5-one (3,7-dibromodibenzo [a, d] cyclohepten-5-one) was replaced. The intermediates, yield and MS analysis at all stages are listed in Table 4 below.

Synthesis of Intermediate B4

Intermediate B4 can be prepared according to Scheme III above.

Intermediate B3 (1.0eq), Intermediate A1 (2.1eq), Pd (OAc) ₂ (0.01eq), P ( t- Bu) ₃ HBF ₄ (0.02eq) and NaO t Bu (1.5) in toluene (0.3M) eq) was heated to 90 ° C. for 12 h. After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL). The mixed organic extracts were washed with brine solution, dried over Na ₂ SO ₄ and concentrated to give a yellow solid. The crude product was also purified by column chromatography on silica gel to give intermediate B4 as a yellow solid in 83% yield.

synthesis Example 3  Intermediates C1 to C7 and their synthesis

Intermediates C1 to C7 for preparing the compounds of formula (I) are listed in Table 5 below.

Synthesis of Intermediate C1

Intermediate C1 is prepared according to Scheme IV above.

Step 1 : Spiro  Alcohol( Spiro  synthesis of alcohol)

To the 2-bromobiphenyl (46 g, 1 eq) in anhydrous THF (0.3 M), n- BuLi (79 mL, 2.5 M, 1 eq) was added dropwise and stirred at -78 ° C. It was. After stirring for 20 minutes, Intermediate B1 (46.3 g, 0.7 eq) was added to the mixture and the reaction mixture was warmed to room temperature. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was washed with water and the water layer was extracted with ethyl acetate. The organic layer was mixed, washed with saturated saline and dried over magnesium sulfate. After drying, the mixture was suction filtration and the filtrate was concentrated. 65 g of spiro alcohol was obtained as a light yellow, powdery solid and used directly in step 2 without further purification.

Step 2 : Synthesis of Intermediate C1

To the obtained spiro alcohol (65 g, 1 eq), acetic acid (w / v = 1/3 for the reaction) and H ₂ SO ₄ (10 drops) were added and the mixture was stirred at 110 ° C. for 6 hours. Was stirred. The reaction was monitored by HPLC. After completion of the reaction, the precipitate was separated by filtration. The residue was purified by column chromatography to give 58 g of intermediate C1 as a white solid in 93.0% yield. FD-MS analysis C ₃₁ H ₁₉ Br: theoretical value 471.39, observed 471.39.

Synthesis of Intermediates C2 and C3

The preparation of intermediates C2 and C3 is similar to the preparation of intermediate C1, except that the 2-bromobiphenyl intermediate and intermediate B used in the preparation of intermediate C1 were replaced with the compounds listed in Table 6 below. It was. The obtained intermediates C2 and C3 were obtained as white solids. In addition, yields and MS analysis data of intermediates C1 to C3 are listed in Table 6 below.

Synthesis of Intermediates C4 and C5

Step 1: Spiro  Synthesis of Alcohol

The process for preparing spiro alcohols of intermediates C4 and C5, except that the 2-bromobiphenyl intermediate and intermediate B used in the preparation of the intermediate C1 are replaced with the compounds listed in Table 7 below, Similar to the preparation method.

Step 2: intermediate C4 and C5  synthesis

Spiro alcohol intermediate (1.0 eq) and p-toluenesulfonic acid (2.0 eq) were refluxed by heating in toluene (10 times as much as spiro alcohol) for 12 hours. After cooling the reaction mixture to room temperature, NaHCO ₃ Quenched with saturated aqueous solution, CH ₂ Cl ₂ Extracted with. The organic layer was washed with water, brine and then anhydrous Na ₂ SO ₄ Dried over. The resulting solution was then concentrated under reduced pressure and purified by column chromatography on silica gel to give intermediates C4 and C5 as white solids. In addition, yields and MS analysis data of intermediates C4 and C5 are listed in Table 7 below.

Synthesis of Intermediates C6 and C7

Intermediates C6 and C7 can be prepared according to Scheme VI above.

Intermediate C (1.0eq), boronic acid (1.1eq), Pd (OAc) ₂ (0.01eq), PPh ₃ (0.04eq), 3.0 M aqueous K ₂ CO ₃ solution (1.5eq) in toluene for 12 hours Heated to 100 ° C. After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL). The mixed organic extracts were washed with brine solution, Na ₂ SO ₄ Dry over phase and concentrate to give a yellow solid. The crude product was also purified by column chromatography on silica gel. In addition, the yields and MS analysis data of the intermediates C6 and C7 are listed in Table 8 below.

synthesis Example  4-compounds (1) to (6), (8) to (13), (15) to (19), (21), (23) and (24)

Compounds (1) to (6), (8) to (13), (15) to (19), (21), (23) and ( 24)  synthesis

Compounds of the invention can be synthesized according to the following schematics VII or VIII.

Briefly, intermediates C1 to C3 and C6 to C7 (1.0eq), intermediates A1 to A13 (1.05eq), Pd (OAc) ₂ (0.005eq), P ( t- Bu) ₃ HBF ₄ (in toluene (40 ml) 0.02 eq) and a mixture of NaO t Bu (1.5 eq) was heated to 90 ° C. for 12 hours (mono- and bis-coupled product was subjected to equivalent weights of intermediates A1 to A13 and catalyst By regioselectively). After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL). The mixed organic extracts were washed with brine solution, Na ₂ SO ₄ Dry over phase and concentrate to give a yellow solid. The crude product was also purified by column chromatography on silica gel to give the final compound as a white solid.

Briefly, intermediates C4 and C5 (1.0 eq), intermediates A14 and A15 (1.2 eq), Pd ₂ (dba) ₃ (0.01 eq), P (Cy) ₃ HBF ₄ (0.04 eq) in toluene (40 ml), and The mixture of K ₃ PO ₄ (3.0eq) was heated to 100 ° C. for 12 hours. After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL). The mixed organic extracts were washed with brine solution, Na ₂ SO ₄ Dry over phase and concentrate to give a yellow solid. The crude product was also purified by column chromatography on silica gel to give the final compound as a white solid.

The products (1) to (6), (8) to (13), (15) to (19), (21), (23) and (24), intermediates used, yields and MS analysis data are shown in the table below. Enumerated in 9.

Example  - OLED  Device fabrication

A glass substrate coated with ITO (Indium Tin Oxide) having a thickness of 1500 kPa was placed in distilled water in which detergent was dissolved, and ultrasonically cleaned. At this time, the detergent is a product manufactured by Fischer, the distilled water was filtered twice through a filter (Millipore). The ITO was washed with detergent for 30 minutes, then ultrasonically washed with distilled water for 10 minutes, washed with isopropyl alcohol, acetone and methanol, dried and then plasma cleaner. (plasma cleaner). Thereafter, the substrate was cleaned with oxygen plasma for 5 minutes and then transferred to a vacuum evaporator.

Various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of this example. The degree of vacuum in the deposition was maintained at ¹ × 10 ⁻⁶ to 3 × 10 ⁻⁷ torr. In addition, the formulas and code names of the materials used in the following OLED devices are listed in Table 10 below.

blue OLED  Manufacture of device

In order to fabricate the blue OLED device of this embodiment, HAT was first deposited on an ITO substrate to form a first hole injection layer having a thickness of 100 kPa. HI-2 was deposited on the first hole injection layer to which a dopant HAT (5.0 wt%) was added to form a second hole injection layer having a thickness of 750 kPa.

HT-1 or a compound of this disclosure is then deposited to form a first hole transport layer HT1 having a thickness of 100 μs; And / or HT-2 or a compound of the present disclosure was deposited to form a second hole transport layer (HT2) having a thickness of 100 GPa.

Thereafter, BH to which dopant BD (3.5 wt%) was added was deposited on the first or second hole transport layer to form a light emitting layer having a thickness of 250 kPa. ET to which dopant Liq (35.0 wt%) was added was deposited on the light emitting layer to form an electron transport layer having a thickness of 250 μs. Liq was deposited on the electron transport layer to form an electron injection layer having a thickness of 15 μs. Al was deposited on the electron injection layer to form a cathode having a thickness of 1500 GPa.

After the above process, the blue OLED device used in the following test was obtained.

green OLED  Manufacture of device

Fabrication of the green OLED device was similar to that of the blue OLED device except for the second hole injection layer, the light emitting layer, and the electron transport layer.

Here, the thickness of the second hole injection layer was 1300 mm 3. GH to which dopant GD (10 wt%) was added was deposited on the first or second hole transport layer to form a light emitting layer having a thickness of 400 GPa. The thickness of the electron transport layer was 350 kPa.

Red OLED  Manufacture of device

Fabrication of the red OLED device was similar to that of the blue OLED device except for the second hole injection layer, the light emitting layer, and the electron transport layer.

Here, the thickness of the second hole injection layer was 2100 kPa. RH to which dopant RD (3.5 wt%) was added was deposited on the first or second hole transport layer to form a light emitting layer having a thickness of 300 GPa. The thickness of the electron transport layer was 350 kPa.

OLED  Device measurement

The performance of the blue, green and red OLED devices obtained above was measured by PR-650. For the blue and red OLED devices, data was collected at 1000 nits. For the green OLED device, data was collected at 3000 nits. Data such as CIE, luminous efficiency (Eff) and driving voltage (Voltage) are listed in Tables 11 to 13 below.

According to the results shown in Tables 11 to 13, the OLED device to which the compound of formula (I) is applied shows improved luminous efficiency and low driving voltage. Therefore, the compound of formula (I) of the present invention can be efficiently used as the hole transporting material of the OLED device.

While the invention has been described in connection with its preferred embodiments, it should be understood that many various possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.

Claims (10)

As a compound,
The compound is represented by one of the following formulas (I-1) to (I-6):

Wherein Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently an unsubstituted C ₁ -C ₂₀ alkyl group, a substituted C ₁ -C ₂₀ alkyl group, an unsubstituted C ₆ -C ₄₀ aryl group A C ₆ -C ₄₀ aryl group substituted with a substituent, an unsubstituted C ₁ -C ₄₀ heterocyclic group, or a C ₁ -C ₄₀ heterocyclic group substituted with a substituent; Or Ar ₁ and Ar ₂ together with the nitrogen atom linking them, form an unsubstituted C ₁ -C ₄₀ heterocyclic group, or a substituted C ₁ -C ₄₀ heterocyclic substituted with; Or Ar ₃ and Ar ₄ together with the nitrogen atom linking them, form an unsubstituted C ₁ -C ₄₀ heterocyclic group, or a substituted C ₁ -C ₄₀ heterocyclic substituted with;
L and Q are each independently selected from unsubstituted C ₆ -C ₄₀ aryl substituted with C ₆ -C ₄₀ aryl group or a substituent group;
G is deuterium, unsubstituted C ₁ -C ₂₀ alkyl group, substituted with a substituent C ₁ -C ₂₀ alkyl, unsubstituted C ₆ -C ₄₀ aryl group, or a C ₆ -C ₄₀ aryl substituted with a substituent group; And
n1 and n2 are each independently 0 or 1;
And the substituent is a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, an aryl group, an arylalkyl group, an aryl alkenyl group, a heterocyclic group, a nitrile group, or an acetylene group. The method of claim 1,
_{Ar 1, Ar 2, Ar 3} , and Ar ₄ are each independently, unsubstituted C ₆ -C ₄₀ aryl, substituted C ₆ -C ₄₀ aryl groups, unsubstituted C ₁ -C ₄₀ heteroaryl as the substituent A cyclic group or a C ₁ -C ₄₀ heterocyclic group substituted with the above substituents; Or Ar ₁ and Ar ₂ together with the nitrogen atom bonded to them form an unsubstituted C ₁ -C ₄₀ heterocyclic group or a C ₁ -C ₄₀ heterocyclic group substituted with the above substituents; Or Ar ₃ and Ar ₄ together with the nitrogen atom bonded to them form an unsubstituted C ₁ -C ₄₀ heterocyclic group or a C ₁ -C ₄₀ heterocyclic group substituted with the above substituents. The method of claim 1,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are each independently an unsubstituted phenyl group, a phenyl group substituted with the substituent, an unsubstituted biphenyl group, a biphenyl group substituted with the substituent, an unsubstituted terphenyl group, and A terphenyl group substituted with a substituent, an unsubstituted fluorenyl group, a fluorphenyl group substituted with the substituent, an unsubstituted tribenzyl oxepinyl group, a tribenzyl oxepinyl group substituted with the substituent, an unsubstituted dibenzofuranyl group, Dibenzofuranyl group substituted with the above substituent, unsubstituted dibenzothiofuranyl group, dibenzothiofuranyl group substituted with the above substituent, unsubstituted naphthyl group, naphthyl group substituted with the above substituent, unsubstituted tribenzyl- A compound which is an azefinyl group or a tribenzyl-azinyl group substituted with said substituent. The method of claim 1,
L and Q are each independently an unsubstituted phenylene group, an unsubstituted biphenylene group, or an unsubstituted naphthylene group, a phenylene group substituted with the substituent, a biphenylene group substituted with the substituent, or the substituent A compound, which is a substituted naphthylene group. The method of claim 1,
G is an unsubstituted C ₆ -C ₄₀ aryl group, or a C ₆ -C ₄₀ aryl group substituted with the substituent, the compound. The method of claim 1,
-L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ are each independently selected from the group consisting of the following compounds:

Wherein * represents the bonding positions,
Ra and Rb are each independently C _1-20 alkyl,
x and y are each independently 1 or 2; The method of claim 1,
-L _n1 -NAr ₁ Ar ₂ and -Q _n2 -NAr ₃ Ar ₄ are each independently selected from the group consisting of the following compounds,

Wherein * represents the bonding positions,
Ra and Rb are each independently a C _1-20 alkyl group,
x and y are each independently 1 or 2; The method of claim 1,
A compound represented by any one of the following compounds (1) to (20) and (23) to (122):

As an organic electronic device,
A first electrode;
Second electrode; And
An organic layer disposed between the first electrode and the second electrode,
The organic electronic device of claim 1, wherein the organic layer comprises the compound of claim 1. delete

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