KR20150065184A - Benzothiophene derivative and use thereof in organic electroluminescent field - Google Patents

Abstract

The present invention relates to a compound represented by formula (I) wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ -C ₃₀ arylamine group, a substituted or unsubstituted C ₄ -C ₄₀ , A substituted or unsubstituted C ₄ to C ₄₀ benzothiophene group or a substituted or unsubstituted C ₄ to C ₄₀ benzofuran group, L is a crosslinking group, a single bond, C ₄ and ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, oxygen atoms, one selected from a nitrogen atom or a sulfur atom of R ₃ -R ₁₀ Are independently selected from the group consisting of H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups or C ₆ -C ₃₀ aromatic groups and are linked to form a ring to form a naphthothiophene derivative, m, n is selected from integers of 0-3 and m + n is greater than 0 and less than or equal to 3; The present invention also protects the use of this type of compound in an organic electroluminescent device, and particularly protects the use of a hole transport material, a hole injection material, or an organic light emitting material as a main material in an OLED device.

Description

BENZOTHIOPHENE DERIVATIVE AND USE THEREOF IN ORGANIC ELECTROLUMINESCENT FIELD BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organic compounds, and more particularly to benzothiophene derivatives used in organic electroluminescent devices and their applications in the field of organic electroluminescence.

Currently, triarylamine derivatives (for example, Patent Publication No. CN 1152607C, published date 2004, 6, 2) are generally used as hole injection and transfer materials in organic electroluminescent devices, Is as follows. As the injection material, for example, it has at least three triarylamine structural units in one molecule as in the structural formula 1, the two N's are separated by a benzene ring; As a transfer material, it usually has two triarylamine structural units in one molecule, and the two N's are separated by biphenyl, and a typical example of this material is NPB.

In recent years, research on this material has made new progress and introduces one or more thienyl groups in the molecule as shown in Structural Formula 3 and Structural Formula 4 (Patent: Publication No. CN101506191A, Publication date: 2009, 8, Or when one or more benzothiophene groups were introduced, the result of the evaluation of the result was that the thienyl group and the benzothiophene group greatly enhanced the hole injection ability of the material. As a transfer material, one of the triarylamine structures in the material, such as the structural formula 5 and the structural formula 6 (patent number: CN102334210A, filing date 2012, 1, 25; Publication No. WO 2010/114017 A1, When the unit was substituted with carbazole or dibenzofuran, the transfer ability of the material was greatly improved.

Therefore, it is very important to develop new stable and highly efficient hole injecting / transporting materials or host materials for the organic light emitting layer to lower the lighting voltage, increase the efficiency of the device, and extend the lifetime of the device.

The present invention provides a benzothiophene derivative substituted with a novel double hole transport group, and the derivative is applied to an organic light emitting functional layer to form a hole transport material and / or a hole injection material And / or an organic electroluminescent device having a low driving voltage and a high luminous efficiency through use as a main material of an organic light emitting layer.

In order to solve the above-mentioned technical problems, the technical scheme used in the present invention is as follows.

Of the benzothiophene materials substituted with the double hole transport group, the official transmission mechanisms of the hole injection material or the hole transfer material are as follows. Since the energy of the lone pair of electrons is the highest in the whole material, it is easy to lose the most because the energy of the lone pair is the highest. Therefore, one electron in the lone pair of N in the material is lost during the injection or transfer of holes to form holes. If a thiophene structural unit is present in the molecule, the lone pair of electrons on the S atom loses electrons and is more likely to form a hole, which is more likely to transfer electrons. The main reason for this is that S is an element of the third period, N is an element of the second period, and the lone electron pair of S is located in the third layer orbit, whereas the lone electron pair on N is located in the second layer orbit , The lone pair of electrons above N is more difficult to lose and S is more easily lost than S, so it is easier to inject and the hole transfer can proceed more easily. Therefore, these materials disclosed by the present invention have at least two S atoms in the molecule, regardless of the structure of the substituent, so that the material easily loses electrons and ensures the transfer of holes.

The benzothiophene material substituted with the double hole transfer group has a relatively high triplet state energy level, a glass transition temperature, and a relatively strong hole transferring ability, The fluorescence quenching caused by agglomeration of the organic light emitting layer can be effectively avoided. These advantages not only make it possible to use the derivative of this type as a hole transport material and / Materials, especially fluorescent blue light, should have the potential to be used as the main material.

The present invention provides a benzothiophene derivative having a structure represented by the following formula (I).

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group of a substituted or unsubstituted C ₄ to C ₄₀ benzofuran group,

L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,

R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and the two adjacent groups are connected to form a ring naphthothiophene , ≪ / RTI > NTH) derivatives,

m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3;

It is preferable that two adjacent groups in R ₃ -R ₁₀ are connected to form a ring to form one or a plurality of ring-closing rings.

The following structural formulas of the above compounds are preferred.

The benzothiophene derivative is used as a hole injecting material and / or a hole transmitting material in an organic electroluminescent device.

The benzothiophene derivative may be used as an organic luminescent material of an organic luminescent layer in an organic electroluminescent device. The organic light emitting material includes a main material and a dye. Specifically, the benzothiophene derivative may be used as a main material in the light emitting layer of the organic electroluminescent device.

The present invention also provides an organic electroluminescent device including a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer, and a cathode layer.

Wherein the material used for the organic emission functional layer includes a hole injection material, a hole transport material, an organic emission material, and an electron transfer material, and the material used for the organic emission functional layer has a compound represented by the following structural formula (I)

Among them.

R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ benzoyl A substituted or unsubstituted benzofuran group, a substituted or unsubstituted C ₄ to C ₄₀ benzofuran group,

L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,

R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &

m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3;

The present invention also provides an organic electroluminescent device including a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer.

Wherein the material used for the organic light emitting functional layer comprises a hole injection material, a hole transfer material, an organic light emitting material, and an electron transfer material, and the hole injection material has a compound represented by the following structural formula (I)

Among them,

R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ benzoyl A substituted or unsubstituted benzofuran group, a substituted or unsubstituted C ₄ to C ₄₀ benzofuran group,

L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,

R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &

m and n are selected from integers of 0 to 3, and m + n is larger than 0 and smaller than 3.

The present invention also provides an organic electroluminescent device including a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer.

Wherein the material used for the organic light emitting functional layer includes a hole injecting material, a hole transmitting material, an organic light emitting material, and an electron transmitting material, and the hole transmitting material has a compound represented by the following structural formula (I)

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group, a substituted or unsubstituted C ₄ -C ₄₀ benzofuran group,

L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,

R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &

m and n are selected from integers of 0 to 3, and m + n is larger than 0 and smaller than 3.

The present invention also provides an organic electroluminescent device including a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer.

Wherein the material used for the organic light emitting functional layer includes a hole injection material, a hole transport material, an organic light emitting material, and an electron transfer material, and the main material of the organic light emitting material contains a compound represented by the following structural formula (I)

Among them,

R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ benzoyl A substituted or unsubstituted benzofuran group, a substituted or unsubstituted C ₄ to C ₄₀ benzofuran group,

L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,

R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &

m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3;

The benzothiophene derivatives of the present invention have the following advantages.

(1) Since the benzothiophene derivative according to the present invention has at least one thienyl group, the isolated electron pair on the S atom loses electrons and tends to form holes, so that the compound is used as a hole injecting and / or transferring material When used, it has a high charge carrier injection and transport capability.

(2) Since the benzothiophene derivatives according to the present invention have a relatively large molecular weight and a relatively large number of branch structures, they have a relatively high glass transition temperature, and therefore the stability of the compound is high and it is very advantageous to further extend the lifetime of the device.

(3) The benzothiophene derivative according to the present invention can be used as a hole injecting and / or hole transporting material and has a high charge carrier injection and transporting ability, which greatly improves the luminous efficiency of the device. Device Embodiments OLED1 to OLED80 show that devices manufactured using the organic compound of the present invention as an organic light emitting functional layer material can effectively lower the driving voltage and improve the current efficiency.

(4) The benzothiophene derivative according to the present invention can also be used as a material for an organic light emitting layer, in particular as a fluorescent blue light main material, and the material according to the present invention can also be mixed with other conventional fluorescent blue light And its molecular orbital energy level is included in the range of the main material energy level, it is advantageous to transfer electrons and holes, and thus the luminous efficiency of the device is greatly improved. Device Examples OLED81 to OLED134 show that devices manufactured using the organic compound of the present invention as an organic light emitting function layer material can effectively lower the driving voltage and improve the current efficiency.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. Among them,
1 is a nuclear magnetic resonance spectrum (NMR) of an intermediate M64-1 of a benzothiophene derivative according to the present invention (1H).
2 is a mass spectrum of a benzothiophene derivative M51 according to the present invention.
3 is a thermal weight loss spectrum of the benzothiophene derivative M51 according to the present invention.
4 is an absorption spectrum of the benzothiophene derivative M51 according to the present invention.
5 is an emission spectrum of the benzothiophene derivative M51 according to the present invention.
6 is a nuclear magnetic resonance spectrum of the benzothiophene derivative M51 according to the present invention (13C).

The benzothiophene, 3-bromo-9-phenyl-carbazole, 9- (4-bromophenyl) -carbazole, 4-bromo- 9-methyl-carbazole, 9- (4-bromophenyl) -3,6-dimethyl-carbazole, diphenylamine, 2-bromodibenzo (b, d) thiophene, 2-bromodibenzo (b, d) furan, Dibromo-dibenzo (b, d) thiophene, 3,7-dibromo-dibenzo (dibromo) dibenzo b, d) thiophene, 2,8-dibromo-dibenzo (b, d) furan, 3,7-dibromo-dibenzo 3,6-dibromo-9- (4-fluoro-phenyl) -methanone, 4-tolyl) -carbazole, 3,6-dibromo-9-ethyl-carbazole, N, N'-diphenylbenzidine, tri- (p-bromophenyl) (Tris (4-bromophenyl) amine) were all purchased and 1 - or 2-aryl substituted benzothiophene and naphthothiophene (Can. J. Chem. 59,227; 59, 1297 (1981)), 3-bromo- (B) thiophene (Adv. Mater. 2007, 19, 3008), 3,3'-dibromo-2,2'-bibenzo (b) 3,3'-dibromo-2,2'-bibenzo (b) thiophene (Adv. Mater. 2007, 19, 3008), 3-chloro- naphtho (1,2- b) thiophene Chemistry of Heterocyclic Compounds, 1983, 156), 1-chloro- naphtho (2,1-b) thiophene (1983, 156), 3,3'- Hanan University, 2009), 2,2'-binaphto (2,3-b) thiophene (J. Mater. Chem., 2008, 18, 3442), and the boric acid derivatives used were all prepared according to literature methods.

Compound synthesis Example

Example 1

Synthesis of Compound M1

The structural formula and the synthesis route of the compound M1 to be produced in this embodiment are as follows.

Under the protection of nitrogen gas to a three-necked flask of 100ml 9- phenyl -9 H - carbazol-3-boric acid, 6.31g (22mmol), 3,3'- dibromo-2,2'-benzo (b) thiophene , 462 mg of tetrakis (triphenylphosphine) palladium, 30 ml of toluene, 10 ml of ethyl alcohol and 5.3 g (50 mmol) of sodium carbonate and 20 ml of water were charged and the mixture was reacted for 3 hours, . The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) led to 5.1 g of white solid, yield 68%.

Example 2

Synthesis of Compound M2

The structural formula and the synthesis route of the compound M2 prepared in this Example are as follows.

In Example 1 it was used as a similar method as equivalents of 4- (9 H-carbazole-9-yl) -9 H 9-phenyl-phenyl boronic acid - replacing carbazol-3-boric acid and other conditions are not changed Compound M2 was obtained under the conditions (white solid, yield 77%).

Example 3

Synthesis of Compound M3

The structural formula and the synthesis route of the compound M3 prepared in this example are as follows.

Example 1 and 4- (diphenylamino) phenyl boric acid, 9-phenyl-equivalent amount of the same was used as a similar method to -9 H - carbazol-3-boric acid and replacing the compound M3 was obtained under the condition the other conditions unchanged ( White solid, yield 65%).

Example 4

Synthesis of Compound M4

The structural formula and the synthesis route of the compound M4 prepared in this example are as follows.

(1) 9-N-tolyl -9 H of the three-necked flask 100ml under the protection of the gas-carbazol-2-boric acid, 3.31g (11mmol), 3,3'- dibromo-2,2'-benzo (b (10 mmol) of thiophene, 462 mg of tetrakis triphenylphosphine palladium, 30 ml of toluene, 10 ml of ethyl alcohol and 5.3 g (50 mmol) of sodium carbonate and 20 ml of water are added and the mixture is reacted for 3 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. The residue was purified by column chromatography (dichloromethane / petroleum ether) to give 4.1 g of a white solid with a yield of 80%.

(2) In a 100 ml three-necked flask under nitrogen gas protection, 2.61 g (9 mmol) of 4- (diphenylamino) phenylboronic acid, 4.1 g (8 mmol) of the above product, (50 mmol) of sodium carbonate and 20 ml of water are added to the mixture, and the mixture is reacted for 3 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 5 g of a white solid, yield 82%.

Example 5

Synthesis of Compound M5

The structural formula and the synthesis route of the compound M5 prepared in this Example are as follows.

(1) Synthesis of Intermediate M5-2: In a 100 ml three-necked flask under nitrogen gas protection, 3.67 g (10 mmol) of M5-1 (preparation method is referred to the method of J. Mater. Chem., 2008, 18, 3442) ) And 50 ml of dichloromethane were charged, and the mixture was reacted. After cooling to 0 ° C, 10 ml of a dichloromethane solution of 3.52 g of liquid bromine was gradually added dropwise thereto, followed by repeatedly stirring for 1 hour at this temperature. After overnight reaction at room temperature, the reaction was stopped by addition of sodium dichromate solution when the indicated result was complete reaction, followed by washing with water. The aqueous phase was extracted, combined with the organic phase, (Spin Dry) to obtain a yellow solid. Column chromatography (dichloromethane / petroleum ether) was followed to yield 3.7 g of white solid M5-2 with a yield of 71%.

(2) 9-phenyl--9 H a 100ml three-necked flask under the protection of nitrogen gas-carbazol-3-boric acid, 6.32g (22mmol), M5-2 5.2g ( 10mmol), tetrakis (triphenylphosphine) palladium 462mg, 30 ml of toluene, 10 ml of ethyl alcohol, 5.3 g (50 mmol) of sodium carbonate and 20 ml of water are added, the mixture is reacted, and the reaction is carried out for 7 hours. The reaction is stopped when the result is complete reaction. After cooling to room temperature, the solution is separated, washed with water, extracted with water, combined with organic phase, and the solvent is spin-dried. The crude product was purified by silica gel column chromatography (dichloromethane / petroleum ether) to give 6.2 g of a white solid with a yield of 73%.

Example 6

Synthesis of Compound M6

The structural formula and the synthesis route of the compound M6 prepared in this Example are as follows.

(2,1-b) thiophene (Chemistry of Heterocyclic Compounds, 1983, 156) and phenylcarbazole with reference to Fu's method (J. Am. Chem. Soc, The Suzuki coupling reaction was carried out using boric acid. Hydrogen was removed from the obtained compound by using butyllithium, and the compound was oxidatively coupled with anhydrous CuCl 2 (J Mate LChem., 2008, 18, 3442) to obtain a compound M6. The yield of the two steps is 28%.

Example 7

Synthesis of Compound M7

The structural formula and the synthesis route of the compound M7 prepared in this example are as follows.

The manufacturing method is as follows.

(1) In a 250 ml three-necked flask, 21.3 g (0.1 mol) of 3-bromo-benzo (b) thiophene and 150 ml of anhydrous ethyl ether were added and cooled to about -78 ° C with a dry ice- acetone cryostat , 44 ml of 2.4 M n-butyl lithium solution (105 mmol) was added dropwise while stirring, and the dropping rate was controlled so that the temperature of the reaction solution did not exceed -70 ° C. After completion of the dropping, the reaction temperature was maintained at -78 ° C. for 1 hour . Next, 16 g of anhydrous sodium chloride (120 mmol) is added in batches. The cryostat is stopped. The temperature is slowly raised to room temperature and the reaction is carried out for 3 hours. The reaction mixture is added to a saturated solution of 400 ml of ammonium chloride, the solution is separated, and the organic phase is washed and dried. The obtained preparation was separated by column chromatography to obtain 7.45 g of a white solid, and the yield was 56%. (2) Synthesis of 2,2'-dibromo-3,3'-bibenzo (b) thiophene.

(2) In a 250 ml three-necked flask, 13.3 g of 3,3'-bibenzo (b) thiophene (0.05 mmol) and 150 ml of anhydrous ethyl ether were added and cooled to about -78 ° C with a dry ice- 44 ml 2.4 M n-butyl lithium solution (105 mmol) was added dropwise while stirring, and the dropping rate was controlled so that the temperature of the reaction solution did not exceed -70 캜. After completion of the dropping, the reaction temperature was maintained at -78 캜 for 1 hour. Next, 21.3 g of solid powder NBS (120 mmol) is added in batches, and the cryostat is stopped. The temperature of the cryostat is slowly raised to room temperature, and the mixture is reacted at room temperature for 3 hours. The reaction mixture is added to a saturated solution of 400 ml of ammonium chloride, the solution is separated, and the organic phase is washed and dried. The obtained preparation was separated by column chromatography to obtain 15.3 g of a white solid, and the yield was 72%.

(3) Synthesis of M7

3,3'-dibromo-2,2'-benzo (b) thiophene and phenyl--9 H - carbazol-3-boric acid, respectively 2,2-dibromo-3,3 ' Biphenol M7 (6.1 g, white solid, 81% yield) was obtained in exactly the same manner as in Example 1, except that (b) thiophene and 4-carbazolephenylboronic acid were used.

Example 8

Synthesis of Compound M8

The structural formula and the synthesis route of the compound M8 prepared in this Example are as follows.

A similar procedure to Example 7 was used, except that 4-carbazolylboronic acid was replaced with the same equivalent of 4- (diphenylamino) phenylboronic acid and the compound M8 (White solid, yield 65%).

Example 9

Synthesis of Compound M9

The structural formula and the synthesis route of the compound M9 prepared in this Example are as follows.

A similar procedure to the first step of Example 5 was used and M5-1 was replaced with M9-1 (prepared according to the method of J. Mater. Chem., 2008, 18, 3442) as starting material and the other conditions Intermediate M9-2 was obtained under unchanged conditions.

Suzuki coupling reaction was performed in two steps according to a method similar to Example 4, M4-1 was substituted for intermediate M9-2, and in the first Suzuki coupling reaction, 3-boric acid-N-phenylcarbazole- -9 H - carbazol-2-boric acid was replaced second Suzuki coupling reaction in the 9-phenyl -9 H - carbazol-2-boric acid by 4- (diphenylamino) it was replaced by phenylboric acid other conditions Compound M9 was obtained under unchanged conditions (white solid, yield 50%).

Example 10

Synthesis of Compound M10

The structural formula and the synthesis route of the compound M10 prepared in this example are as follows.

Preparation of intermediate M10-1: Intermediate M10-1-1 was obtained through intermediate NPS bromination reaction to obtain intermediate M10-1-2 and Buchwald coupling with diphenylamine to obtain intermediate M10-1-3 Butyl lithium was used to remove hydrogen to obtain a lithium salt. After reacting with triisopropyl borate, acid decomposition was performed to obtain boric acid M10-1.

Preparation of intermediate M10-2: Intermediate M10-2-1 was prepared by removing hydrogen from n-butyllithium, obtaining lithium salt, reacting with triisopropyl borate and acid-decomposing to obtain boric acid M10-2-2 -Bromo-N-ethylcarbazole was subjected to Suzuki coupling reaction to obtain intermediate M10-2-3, followed by NBS bromination to obtain intermediate M10-2.

Intermediates M10-1 and M10-2 undergo Suzuki coupling to give compound M10 (white solid, yield 30%).

Example 11

Synthesis of compound M11

The structural formula and the synthesis route of the compound M11 prepared in this example are as follows.

Example 4 was used as a similar way to 9-tolyl -9 H-carbazole-3-boric acid and 4- (diphenylamino) of equivalent weight of phenylboric acid, respectively 4-carbazole-phenylboronic acid there was obtained dimethyl-4-carbazole The compound M11 was obtained (solid white, yield: 45%) under the condition that the compound was replaced with zeolite and the other conditions were not changed.

Example 12

Synthesis of Compound M12

The structural formula and the synthesis route of the compound M12 prepared in this example are as follows.

Synthesis of intermediate M12-1: After Suzuki coupling reaction of 2,3-dibromobenzothiophene with 4- (diphenylamino) phenylboric acid, intermediate M12-1-1 was obtained, followed by a conventional preparation method of boric acid Thus obtaining an intermediate M12-1.

Synthesis of Intermediate M12-2 Intermediate M12-2-1 was obtained via an NBS bromination reaction to obtain intermediate M12-2-2 and Suzuki coupling reaction with intermediate M12-2-3 to obtain intermediate M12-2- 4 was obtained, followed by NBS bromination to obtain intermediate M12-2.

Intermediates M12-1 and M12-2 were subjected to Suzuki coupling reaction to give compound M12 (caustic solid, yield 33%).

Example 13

Synthesis of Compound M13

The structural formula and the synthesis route of the compound M13 prepared in this example are as follows.

Compound M13 was prepared (white solid, yield 57%) by reference to the preparation of compound M7 in Example 7, except that the synthetic procedure was the replacement of 3-boronic-N-phenylcarbazole with 4-carbazolephenylboronic acid. .

Example 14

Synthesis of compound M14

The structural formula and the synthesis route of the compound M14 prepared in this example are as follows.

Compound M14 was prepared with reference to the preparation of compound M7 in Example 7, except that 4-carbazolylboronic acid was substituted for dibenzothiophene-2-boronic acid (white solid, yield 61% ).

Example 15

Synthesis of compound M15

The structural formula and the synthesis route of the compound M15 prepared in this example are as follows.

Carried out in Example 1 using 3-phenyl-2-benzo (b) the equivalent amount of the same were to use a similar method thiophene acid 9-phenyl -9 H - carbazol-3-boric acid under the condition replaced and the other conditions unchanged Chemistry Water M15 (white solid, yield 78%).

Example 16

Synthesis of compound M16

The structural formula and the synthesis route of the compound M16 prepared in this Example are as follows.

Compound M16, a white solid, was fully prepared with reference to the preparation of compound M5 in Example 5, except that the synthetic procedure was simply modified with the corresponding boric acid. Mass spectrum and elemental analysis results are listed in the attached table.

Example 17

Synthesis of Compound M17

The structural formula and the synthesis route of the compound M17 prepared in this example are as follows.

Examples 1 and dibenzo of equivalents was used as a similar method (b, d) thiophene-2-boric acid with 9-phenyl--9 H - carbazol-3-boric acid and substitution compound under conditions and other conditions are not changed M17 (white solid, yield 78%).

Example 18

Synthesis of compound M18

The structural formula and the synthesis route of the compound M18 prepared in this Example are as follows.

Examples 1 and dibenzo of equivalents was used as a similar method (b, d) thiophen-3-boric acid with 9-phenyl--9 H - carbazol-3-boric acid and substitution compound under conditions and other conditions are not changed M18 (white solid, yield 67%).

Example 19

Synthesis of compound M19

The structural formula and the synthesis route of the compound M19 prepared in this example are as follows.

Examples 1 and dibenzo of equivalents was used as a similar method (b, d) furan-2-boric acid with 9-phenyl--9 H - carbazol-3-boric acid and replacing the compound in the situation other conditions unchanged M19 (White solid, yield 56%).

Example 20

Synthesis of compound M20

The structural formula and the synthesis route of the compound M20 prepared in this example are as follows.

Examples 1 and dibenzo of equivalents was used as a similar method (b, d) furan-3-boric acid with 9-phenyl--9 H - replacing carbazol-3-boric acid compound, and under the condition the other conditions unchanged M20 (White solid, yield 71%).

Example 21

Synthesis of compound M21

The structural formula and the synthesis route of the compound M21 prepared in this example are as follows.

    The synthesis of intermediate M21-1 is described in the Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1972, p. 556-559.

M21-1 is obtained by extracting hydrogen using n-butyllithium to obtain a lithium salt, followed by homocoupling reaction under the action of cupric chloride to obtain intermediate M21-2, followed by NBS bromination to obtain intermediate M21-3 And subjected to Suzuki coupling reaction with 4- (diphenylamino) phenylboric acid to obtain compound M21 (white solid, yield 65%).

Example 22

Synthesis of compound M22

The structural formula and the synthesis route of the compound M22 prepared in this Example are as follows.

(B) thiophene-3-phenol (15 g, 100 mmol, 1 eq) (WO2011 / 61214A1 or. Am. Chem. Soc., 2007, 129, 2704 ) Was cooled to -20 ° C, 2.4M n-butyllithium solution (42ml, 110mmol) was added slowly, and after multiplying, the temperature was slowly raised to room temperature, and after 10 minutes Lt; / RTI > Next, 4.0 ml of a 10% solution of tri-tert-butylphosphine in toluene (2 mmol, 2% eq), 0.58 g of Pd (dba) 2 (1 mmol, 1% eq), and 3-bromo-benzo (b) thiophene 21.3 g, and the reaction system was heated to reflux. After reacting at this temperature for 2 hours, the reaction was quenched by TLC. When the reaction was complete reaction, water (100 ml) was added to stop the reaction. The aqueous phase is extracted with DCM (50 ml). The combined organic phases were washed with saturated brine (100 ml), dried over anhydrous magnesium sulfate and filtered. After drying under reduced pressure (spin drying), a brown oily substance was obtained. After dissolving in DCM, the sample is stirred with silica gel and loaded by dry method. PE / EtOAc system column chromatography to give 24 g of a white solid, yield 85%.

(2) In a 500 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, 14.1 g (50 mmol) of M22-1 and 250 ml of dried THF were added, cooled to -78 ° C, 22 ml (55 mmol) And the solution was changed from yellow to dark black. The reaction was maintained at -60 ° C for 1 hour, cooled to -78 ° C, and 12 g (60 mmol) of solid powder NBS was added thereto. The solution turned yellow and stirred overnight . The reaction mixture was stirred for 30 minutes, and the aqueous phase was extracted. The organic phase was combined, dried over anhydrous magnesium sulfate, and then dehydrated by rotary evaporation. The residue was recrystallized from petroleum ether and filtered to obtain 17 g of a pale white solid And the yield is 80%.

(3) M22-2 to the three-necked flask 250ml under nitrogen protection at room temperature, and magnetic stirring (8.8g, 20mmol, 1eq), 9- phenyl -9 H - carbazol-3-boric acid (12.6g, 44mmol, 2.2eq) Pd (PPh3) 4 (468 mg, 0.41 mmol, 2% eq) is added to a suspension of toluene / EtOH / H2O (50 ml / 50 ml / 50 ml) in which Na2CO3 (10.6 g, 100 mmol, 2.5 eq) is dissolved. After heating to reflux and warming and reacting for 3 h (the system gradually evolves from suspension as the retention time is extended), and when the results of the TLC are complete, spin-spin spin-dry and add EtOAc (150 ml), washed with water (80 ml) and the aqueous phase is extracted with EtOAc (50 ml). The combined organic phases were washed with saturated brine (100 ml), dried over anhydrous magnesium sulfate and filtered. The oil phase was obtained by spin drying under reduced pressure. After dissolving in DCM, the sample is stirred with silica gel. 10.5 g of a white solid was obtained by column chromatography, and the yield was 69%.

Example 23

Synthesis of compound M23

The structural formula and the synthesis route of the compound M23 prepared in this example are as follows.

A carbazole-2-phenyl-boric acid -9 H - - Example 22 with the equivalent of 9-phenyl--9 H of the same was used as a similar method to replace the carbazole-3-boric acid and give the compound M23 (a white solid, Yield 64%).

Example 24

Synthesis of compound M24.

Example 22 and was used in a similar manner 4- (diphenylamino) phenyl boric acid with the same equivalent of 9-phenyl--9 H - carbazol-3-boric acid and replacing the compound M24 was obtained (white solid, yield 69%) .

Example 25

Synthesis of compound M25

Example 22 and was used in a similar manner with the same equivalent of 4-carbazol-9-phenyl-boronic acid -9 H - carbazol-3-boric acid and replacing the compound M25 was obtained (white solid, 80% yield).

Example 26

Synthesis of compound M26

The structural formula and the synthesis route of the compound M26 prepared in this Example are as follows.

(1) Synthesis of intermediate M26-1

(100 mmol) of 3-bromo-benzo (b) thiophene, 3.8 g (50 mmol) of mercaptoc acetic acid, 25.5 g (120 mmol) of potassium phosphate and 100 ml of toluene were placed in a three-necked flask equipped with a condenser tube under the protection of nitrogen gas. (5 mmol, 5% eq) of Pd (dba) and 3.9 g (7 mmol) of dppf were added and the reaction mixture was heated and refluxed for 10 hours, then cooled and saturated ammonium chloride solution was added After the reaction was stopped, the organic phase was separated and the aqueous phase was extracted twice with ethyl acetate. The organic phase was combined, dried over anhydrous magnesium sulfate and swab-off until the solvent was dried to obtain a yellow oily substance. The crude product was separated by silica gel column chromatography to give 8.3 g of a white solid with a yield of 56%.

The remaining steps are carried out, see the Example 22 and 9-phenyl -9 H 4- (diphenylamino) phenyl boric acid with the same equivalent weight-carbazol-3-boric acid and replacing the compound M26 was obtained (white solid, 75% yield) .

Example 27

Synthesis of compound M27

A similar method to Example 26 was used, replacing 4- (diphenylamino) phenylboric acid with the equivalent of 4-carbazole phenylboronic acid to give compound M27 (white solid, yield 80%).

Example 28

Synthesis of compound M28

The structural formula and the synthesis route of the compound M28 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic step is an embodiment identical to the compound M30 and a third step of 30 was with reference to synthesis of compounds M30 one kinds of one kinds of the raw material of which 9-phenyl -9 H-carbazole-3-acid to 4- (Diphenylamino) phenylboric acid, the white solid product was obtained in the absence of other reagents, solvents and reaction conditions.

Example 29

Synthesis of compound M29

The structural formula and the synthesis route of the compound M29 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic step is an embodiment identical to the compound M30 and a third step of 30 was with reference to the process for producing the compound 9-phenyl-M30 one kinds of the raw material of which -9 H-9-a-carbazol-3-boric acid ( 9 H -carbazole) phenyl-4-boric acid, the white solid product was obtained in the absence of other reagents, solvents and reaction conditions.

Example 30

Synthesis of compound M30

The structural formula and the synthesis route of the compound M30 prepared in this embodiment are as follows.

Manufacturing method:

(1) Synthesis of intermediate M30-1

(100 mmol) of 3-bromo-benzothiophene, 4.19 g (45 mmol) of phenylamine, 14.4 g (150 mmol) of sodium tert-butoxide and 300 ml of toluene were placed in a three- After the addition, 20.54 g of Pd (dba) and 34 ml of 10% P (t-Bu) were added and the reaction mixture was heated to reflux reaction for 10 hours, then cooled and water was added to quench the reaction, The mixture was extracted twice with ethyl acetate, and the organic phase was combined, dried over anhydrous magnesium sulfate and swab-off until the solvent was dried to obtain a yellow oily substance. Petroleum ether was then added until the solid precipitated The resulting solid was filtered, washed with methyl alcohol and petroleum ether, and then dried to obtain 13.2 g of a white solid. The yield was 74%.

(2) Synthesis of intermediate M30-2

17.9 g (0.05 mmol) of M30-2 and 150 ml of anhydrous ethyl ether were placed in a 250 ml three-necked flask and cooled to about -78 ° C with a dry ice-acetone cryostat. 44 ml of a 2.4 M n-butyl lithium solution ) And the dropping rate is controlled so that the temperature of the reaction solution does not exceed -70 DEG C, and the reaction temperature is kept at -78 DEG C for 1 hour. Next, 21.3 g (120 mmol) of solid powder NBS was added in batches, and the mixture was added. After the cryostat was stopped, the temperature was slowly raised to room temperature, and the reaction was allowed to proceed at room temperature for 3 hours do. The reaction mixture is added to a saturated solution of 400 ml of ammonium chloride, the separation is carried out, and the organic phase is washed and dried. The obtained preparation was separated by column chromatography to obtain 20.6 g of a white solid, and the yield was 80%.

(3) Synthesis of compound M30

9-phenyl-N -9 H of the three-necked flask 100ml under the protection of the gas-carbazol-3-boric acid, 6.31g (22mmol), M30-2 5.15g ( 10mmol), tetrakis (triphenylphosphine) palladium 462mg, toluene 30ml, 10 ml of ethyl alcohol, 5.3 g (50 mmol) of sodium carbonate and 20 ml of water are added, the mixture is reacted and the reaction is carried out for 3 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 5.71 g of a white solid, yield 68%.

Example 31

Synthesis of compound M31

The structural formula and the synthesis route of the compound M31 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic step is an embodiment identical to the compound M30 and a third step of 30 was with reference to synthesis of compounds of 9-phenyl-M30 one kinds of raw materials of them -9 H-9-a-carbazol-3-boric acid phenyl -9 H -carbazole-2-boric acid, the white solid product was obtained in the absence of other reagents, solvents and reaction conditions.

Example 32

Synthesis of compound M32

The structural formula and the synthesis route of the compound M32 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic step is an embodiment identical to the compound M30 and a third step of 30 was with reference to synthesis of compounds of 9-phenyl-M30 one kinds of raw materials of them -9 H -benzo the di-carbazol-3-boric acid T A white solid product was obtained under the conditions that the other reagents, solvents and reaction conditions were not changed except for the replacement with opene-2-boric acid.

Example 33

Synthesis of compound M33

The structural formula and the synthesis route of the compound M32 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic steps are the same as compounds M30 of Example 30, and the third step was the synthesis of the reference compound 9-phenyl-M30 one kinds of the raw material of which -9 H-carbazole-3-D The acid benzofuran -2-boric acid, the white solid product was obtained in the absence of other reagents, solvents and reaction conditions.

Example 34

Synthesis of compound M34

The structural formula and the synthesis route of the compound M34 prepared in this Example are as follows.

Manufacturing method:

The first two steps in the synthetic step is an embodiment identical to the compound M30 and the third stage 30 is a 9-phenyl -9 H reference was one kinds of raw material of which the synthesis of the compound M30 - carbazol-3-a 3-phenyl-boric acid Benzothiophene-2-boric acid, the white solid product was obtained under the conditions that the other reagents, solvents and reaction conditions were not changed.

Example 35

Synthesis of compound M35

The structural formula and the synthesis route of the compound M35 prepared in this example are as follows.

(1) Synthesis of M35-1

(1) In a 500 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, 25.8 g (100 mmol) of 4,4'-diphenyl ether di-hypoboric acid 3-borate-N-phenylcarbazole, 51 g (220 mmol) of pentene, 3.5 g of tetrakistriphenylphosphine palladium, 150 ml of toluene, 50 ml of ethyl alcohol, 53 g of sodium carbonate and 100 ml of water were charged and the reaction was carried out for 2 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 27.8 g of a white solid, yield 64%.

(2) Synthesis of M35-2

22 g (50 mmol) of M35-1 and 250 ml of dried THF were added to a 500 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas flow, cooled to -78 ° C and 44 ml (105 mmol) of 2.4 M n- After changing from tan to dark black, the reaction was maintained at -60 캜 for 1 hour, cooled to -78 캜, and 23 g (120 mmol) of solid powder NBS was added to the solution to change its color from jade green to yellow, . After saturated aqueous ammonium chloride solution was added, the mixture was stirred for 30 minutes. The aqueous phase was extracted, and the aqueous phase was extracted. The organic phase was combined, dried with anhydrous magnesium sulfate, and subjected to rotary dehydration and recrystallization with petroleum ether. To give 35.3 g of a pale white solid, with a yield of 60%.

(3) Synthesis of compound M35

(22 mmol) of 4-carbazolylphenylboronic acid, 5.9 g (10 mmol) of M35-2, 0.5 g of tetrakistriphenylphosphine palladium, 80 ml of toluene, 40 ml of ethyl alcohol, sodium carbonate And 50 ml of water, and the reaction is carried out for 2 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 5.4 g of a white solid, yield 59%.

Example 36

Synthesis of Compound M36

The structural formula and the synthesis route of the compound M36 prepared in this example are as follows.

Manufacturing method:

The first two steps in the synthetic step is the same as in Example 35 compounds of M35 and a third step the compound was reference to the M35 method of synthesizing 9-phenyl-a -9 H, 4-carbazol-phenylboronic acid one kinds of raw materials of them - carbazol -3-boric acid, the white solid product was obtained in the absence of other reagents, solvents and reaction conditions.

Example 37

Synthesis of Compound M37

The structural formula and the synthesis route of the compound M37 prepared in this example are as follows.

Manufacturing method:

(1) Synthesis of M37-1

(1) Under a nitrogen gas atmosphere, a 500 ml three-necked flask equipped with a mechanical stirrer was charged with 43.4 g (150 mmol) of 4- (diphenylamino) phenylboric acid, 25.4 g (120 mmol) of 3-bromo-benzothiophene, 2 g of phenylphosphine palladium, 150 ml of toluene, 50 ml of ethyl alcohol, 35 g of sodium carbonate and 100 ml of water are added and the reaction is carried out for 2 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. The residue was purified by column chromatography (dichloromethane / petroleum ether) to obtain 36.2 g of a white solid and the yield was 80%.

(2) Synthesis of M37-2

18.9 g (50 mmol) of M37-1 and 250 ml of dried THF were charged into a 500 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, cooled to -78 ° C, 22 ml (53 mmol) of 2.4 M n- After changing from tan to dark black, the reaction was maintained at -60 캜 for 1 hour, cooled to -78 캜, and 11.5 g (60 mmol) of solid powder NBS was added to the solution to change the color from yellow to green, followed by overnight stirring . The reaction mixture was stirred for 30 minutes to separate the phases. The aqueous phase was extracted, and the organic phase was combined. The organic phase was dried with anhydrous magnesium sulfate, and then dehydrated by rotation, recrystallized with petroleum ether, Filtration gave 15.9 g of a white solid with a yield of 70%.

(3) Synthesis of compound M37

(22 mmol) of 4,4'-diphenyl ether dihydrogenphosphoric acid 3-boric acid, 20 g (44 mmol) of M37-2, 2 g of tetrakistriphenylphosphine palladium, 100 ml of toluene, 60 ml of ethyl alcohol, 16 g of sodium carbonate and 80 ml of water are added and the reaction is carried out for 2 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 13.0 g of a white solid with a yield of 64%.

Example 38

Synthesis of Compound M38

The structural formula and the synthesis route of the compound M38 prepared in this example are as follows.

As a synthesis step, reference is made to the synthesis method of compound M37 of Example 37, except that one of the raw materials 4- (diphenylamino) phenylboric acid was replaced with 9- ( 9H -carbazole) phenyl- And the white solid product was obtained under the condition that other reagents, solvents and reaction conditions were not changed.

Example 39

Synthesis of compound M39

The structural formula and the synthesis route of the compound M39 prepared in this example are as follows.

The first two steps of the synthesis step are the same as the compound M64 of Example 64, and the third step refers to the method of synthesizing the compound M64. Among them, 3,3'-dibromo-2,2'-bibenzo b) A white solid product was obtained under the conditions that thiophene was replaced with 2,8-dibromo-dibenzothiophene and the other reagents, solvent and reaction conditions were not changed.

Example 40

Synthesis of compound M40

The structural formula and the synthesis route of the compound M40 prepared in this example are as follows.

The synthesis step refers to the synthesis step of compound M64 of Example 64, and one of the raw materials, 9-Phenyl-9H-Carbazol-3-Ylboronic Acid, was reacted with 4- (diphenylamino ) Phenylboric acid. In the third step, 3,3'-dibromo-2,2'-bibenzo (b) thiophene, which is one of the raw materials, is reacted with 2,8-dibromo-dibenzothiophene And other solid reagents, solvents and conditions under which the reaction conditions were not changed.

Example 41

Synthesis of compound M41

The structural formula and the synthesis route of the compound M41 prepared in this Example are as follows.

The synthesis step refers to the synthesis step of compound M35 of Example 35, and one of the 4,4'-diphenyl ether di-hypobromous acid, which is one of the raw materials, is replaced by 3,7-diboric acid-dibenzothiophene. In the third step One of them, 9- (9H-carbazole) phenyl-4-boric acid was replaced by 4- (diphenylamino) phenylboric acid and a white solid product was obtained under the condition that the other reagents, solvent and reaction conditions were not changed.

Example 42

Synthesis of compound M42

The structural formula and the synthesis route of the compound M42 prepared in this example are as follows.

The synthesis step refers to the synthesis step of compound M35 of Example 35, and one of the raw materials, 4,4'-diphenyl ether di-hypoboric acid, is replaced with 2,8-diboric acid-dibenzothiophene, and in the third step One of them, 9- (9H-carbazole) phenyl-4-boric acid was replaced by 4- (diphenylamino) phenylboric acid and a white solid product was obtained under the condition that the other reagents, solvent and reaction conditions were not changed.

Example 43

Synthesis of Compound M43

The structural formula and the synthesis route of the compound M43 prepared in this example are as follows.

The first two steps of the synthesis step are the same as the compound M64 of Example 64, and the third step refers to the production method of the compound M64. One of the raw materials, 3,3'-dibromo-2,2'-bibenzo b) The thiophene was replaced by 3,7-dibromo-dibenzothiophene and a white solid product was obtained under the conditions that the other reagents, solvents and reaction conditions were not changed.

Example 44

Synthesis of Compound M44

The structural formula and the synthesis route of the compound M44 prepared in this example are as follows.

The first two steps of the synthesis step are the same as the compound M64 of Example 64, and the third step refers to the production method of the compound M64. One of the raw materials, 3,3'-dibromo-2,2'-bibenzo b) A white solid product was obtained under the conditions that the thiophene was replaced with 2,8-dibromo-dibenzofuran and the other reagents, solvents and reaction conditions were not changed.

Example 45

Synthesis of compound M45

The structural formula and the synthesis route of the compound M45 prepared in this Example are as follows.

In the synthesis step, reference is made to the compound M35 of Example 35, and 4,4'-diphenyl ether di-hypoboric acid, which is one of the raw materials, is replaced by 2,8-diboric acid-dibenzofurane. In the third step, (9H-carbazole) phenyl-4-boric acid was replaced by 4- (diphenylamino) phenylboric acid and a white solid product was obtained under the conditions that the other reagents, solvents and reaction conditions were not changed.

Example 46

Synthesis of Compound M46

The structural formula and the synthesis route of the compound M46 prepared in this example are as follows.

The first two steps of the synthesis step are the same as the compound M64 of Example 64, and the third step refers to the method of synthesizing the compound M64. Among them, 3,3'-dibromo-2,2'-bibenzo b) The thiophene was replaced by 3,7-dibromo-dibenzofuran and a white solid product was obtained under the conditions that the other reagents, solvents and reaction conditions were not changed.

Example 47

Synthesis of compound M47

The structural formula and the synthesis route of the compound M47 prepared in this example are as follows.

A similar procedure to Example 64 was used, except that 3-boric acid-N-phenylcarbazole and 3,3'-dibromo-2,2'-bibenzo (b) -Methylphenylcarbazole with 3,6-dibromo-9-phenyl-9H-carbazole and under the same conditions that did not change other conditions, compound M47 was obtained (white solid, yield 56%).

Example 48

Synthesis of compound M48

The structural formula and the synthesis route of the compound M48 prepared in this Example are as follows.

The synthesis step refers to the method for synthesizing the compound M45 of Example 45, except that 4,4'-diphenyl ether di-hypoboric acid, which is one of the raw materials, is replaced by the dihyiphoboric acid shown and the other reagents, Under the circumstances, a white solid product was obtained and the synthesis yield was 76%.

Example 49

Synthesis of compound M49

The structural formula and the synthesis route of the compound M49 prepared in this example are as follows.

(1) Synthesis of M49-1

(1) Under a nitrogen gas atmosphere, 12.2 g (100 mmol) of phenylboronic acid, 42.4 g (100 mmol) of 3,3'-dibromo-2,2'-bibenzo (b) thiophene, 2.3 g of triphenylphosphine palladium, 150 ml of toluene, 100 ml of ethyl alcohol, 27 g (250 mmol) of sodium carbonate and 120 ml of water are added and the reaction mixture is stirred for 3 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 21 g of a white solid with a yield of 50%.

(2) Synthesis of intermediate M49-2

42 g (100 mmol) of M49-1 and 500 ml of dried THF were charged into a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, cooled to -78 ° C and 50 ml (120 mmol) of 2.4 M n- After changing from yellowish brown to dark black, the reaction was carried out at -78 ° C for 1 hour, and then 30 g (159.5 mmol) of triisopropyl borate was added dropwise at -78 ° C. to change the solution from jade green to yellow. After acidification by adding 100 ml of hydrochloric acid at a ratio of 1: 1, the organic phase was separated, washed, dried and evaporated to dryness by distillation. Petroleum ether was added to disperse it, ultrasonication was performed, 28.8 g of a white solid were obtained and the yield was 75% and used directly in the next step.

(3) Synthesis of compound M49

(22 mmol) of M49-2, 4 g (10 mmol) of di- (p-bromobenzene) phenylamine, 0.5 g of tetrakistriphenylphosphine palladium, 80 ml of toluene, 80 ml of ethyl alcohol , 5.3 g of sodium carbonate and 50 ml of water are added and the reaction is carried out for 4 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. The residue was purified by column chromatography (dichloromethane / petroleum ether) to obtain 5.8 g of a white solid, the yield being 63%.

Example 50

Synthesis of Compound M50

The structural formula and the synthesis route of the compound M50 prepared in this example are as follows.

The synthesis step refers to the method of synthesis of compound M48 of Example 48 and substitutes 4- (diphenylamino) phenylboric acid, one of the raw materials in the third step, with dibenzo (b, d) thiophene- In the absence of other reagents, solvents and reaction conditions, a white solid product was obtained with a yield of 68%.

Example 51

Synthesis of Compound M51

The structural formula and the synthesis route of the compound M51 prepared in this Example are as follows.

Example 64 was used with a similar method with the same equivalent of 3,6-dibromo-9-phenyl -9 H - carbazol sol 3,3'-dibromo-2,2'-benzo (b) thiophene To give compound M51 (white solid, yield 45%).

Example 52

Synthesis of compound M52

The structural formula and the synthesis route of the compound M52 prepared in this Example are as follows.

All the specific reaction steps refer to the preparation of Compound 51 in Example 51 and substitute 3-bromobenzothiophene as the starting material with 3-bromonaphtho (2,3-b) thiophene and all other conditions are changed Compound M52 was obtained (white solid, yield 22%).

Example 53

Synthesis of Compound M53

The structural formula and the synthesis route of the compound M53 prepared in this Example are as follows.

All of the specific reaction steps refer to the preparation of Compound 51 in Example 51, substituting 3-boric acid-N-phenylcarbazole with 2-boric acid-N-phenylcarbazole and obtaining compound M53 under the condition that all other conditions are not changed (White solid, 55% yield).

Example 54

Synthesis of compound M54

The structural formula and the synthesis route of the compound M54 prepared in this Example are as follows.

All of the specific reaction steps refer to the preparation of Compound 51 in Example 51 and substitute 3-bromobenzothiophene as 3-bromobenzothiophene as the starting material with 3-bromonaphtho (1,2-b) Compound M54 was obtained under the condition that 6-dibromo-9-phenyl-9H-carbazole was replaced with 3,6-dibromo-9-ethyl-9H-carbazole and all other conditions were unchanged (white solid, yield 27%).

Example 55

Synthesis of Compound M55

The structural formula and the synthesis route of the compound M55 prepared in this example are as follows.

(1) Synthesis of intermediate M55-1: In a three-necked flask equipped with a condenser tube under nitrogen gas protection, 21.3 g (100 mmol) of 3-bromobenzothiophene, 16.9 g (110 mmol) of chlorophenylboronic acid and 26.5 g ), 150 ml of toluene, 80 ml of ethyl alcohol and 100 ml of water are added, and then 2.3 g of Pd (PPh3) 4 is added. The reaction mixture is heated and the reaction is carried out for 10 hours. After cooling, water was added to quench the reaction, and the organic phase was separated. The aqueous phase was extracted twice with ethyl acetate. The organic phase was combined, dried over anhydrous magnesium sulfate, and swab-off until the solvent was dried to obtain a yellow oily substance The resulting solid was filtered, washed with methyl alcohol and petroleum ether, and dried to obtain 20.5 g of white solid M55-1. The yield was 84%.

(2) Synthesis of intermediate M55-2

Under the nitrogen gas protection, 12.2 g (50 mmol) of M55-1 and 250 ml of dried THF were added to a 500 ml three-necked flask equipped with a mechanical stirrer and cooled to -78 ° C and 22 ml (55 mmol) of 2.4 M n- After the solution turns from yellowish brown to dark black, the reaction is maintained at -60 캜 for 1 hour, cooled to -78 캜, and 12 g (60 mmol) of solid powdered NBS is added thereto. After saturated aqueous ammonium chloride solution was added for cancellation, the mixture was stirred for 30 minutes and separated. The aqueous phase was extracted, and the organic phase was combined, dried with anhydrous magnesium sulfate, dispersed with petroleum ether, and subjected to ultrasonic treatment. 14 g of a pale white solid were obtained and the yield was 83%.

(3) Preparation of intermediate M55-3

(100 mmol) of M55-2, 31.6 g (110 mmol) of 9-phenyl-9H-carbazole-3-boric acid, 2.5 g of tetrakistriphenylphosphine palladium, 1500 ml of toluene, 80 ml of ethyl alcohol, 25 g of sodium carbonate and 100 ml of water are added and the reaction is carried out for 4 hours. The reaction was stopped when the result was complete reaction. After cooling to room temperature, it was separated, washed with water, extracted with water, combined with organic phase, dried and spin-dried to obtain yellow oil The phase material was obtained. Column chromatography (dichloromethane / petroleum ether) was followed to yield 34.5 g of a white solid, yield 71%.

(4) Synthesis of compound M55

53.5g (110mmol) of M55-3, 16.8g (50mmol) of N-phenylbenzidine, 14.4g (150mmol) of sodium tert-butoxide and 300ml of toluene were added to a three-necked flask equipped with a condenser tube under the protection of nitrogen gas 0.54 g of Pd (dba) 2 and 4 ml of 10% P (t-Bu) 3 were added and the reaction mixture was heated to reflux for 10 hours. After cooling, water was added to quench the reaction, After extracting with ethyl acetate twice, the organic phase was combined, dried over anhydrous magnesium sulfate, and swab-off until the solvent was dried to obtain a yellow oily substance. Petroleum ether was added thereto to shake the solid until precipitation The resulting solid was filtered, washed with methyl alcohol and petroleum ether, and dried to obtain 42.6 g of a white solid compound M55 (yield 69%).

Example 56

Synthesis of compound M56

The structural formula and the synthesis route of the compound M56 prepared in this Example are as follows.

(1) Synthesis of intermediate M56-1: In a three-necked flask equipped with a condenser tube under the protection of nitrogen gas, 21.3 g (100 mmol) of 3-bromobenzothiophene, 31.8 g (110 mmol) 26.5 g (250 mmol) of sodium carbonate, 150 ml of toluene, 80 ml of ethyl alcohol and 100 ml of water are added, and then 2.3 g of Pd (PPh3) 4 is added. The reaction mixture is heated and the reaction is carried out for 10 hours. After cooling, water was added to quench the reaction, and the organic phase was separated. The aqueous phase was extracted twice with ethyl acetate. The organic phase was combined, dried over anhydrous magnesium sulfate, and swab-off until the solvent was dried to obtain a yellow oily substance The resulting solid was filtered, washed with methyl alcohol and petroleum ether, and dried to obtain 29.9 g of white solid M56-1 at a yield of 79%.

(2) Synthesis of compound M56

A. Under a nitrogen gas atmosphere, 38 g (100 mmol) of M56-1 and 500 ml of dried THF were charged into a 1000 ml three-necked flask equipped with a mechanical stirrer, cooled to -78 ° C and 50 ml (120 mmol) of 2.4 M n- After the solution turned from yellowish brown to dark black, the reaction was maintained at -60 ° C for 30 minutes, cooled to -78 ° C, and 30 g (159.5 mmol) of triisopropyl borate was added dropwise. The solution was then warmed to room temperature, . After saturated aqueous ammonium chloride solution was added, the mixture was stirred for 30 minutes and separated. The aqueous phase was extracted, and the organic phase was combined, dried with anhydrous magnesium sulfate, dispersed with petroleum ether and filtered to obtain a white solid And then used directly in the next step reaction.

B. In a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, 9.6 g (20 mmol) of the above-prepared starting material (100 mmol), tri- (p-bromophenyl) amine, 1.2 g of tetrakistriphenylphosphine palladium , 300 ml of toluene, 120 ml of ethyl alcohol, 52 g of sodium carbonate and 200 ml of water were added and the mixture was reacted at 70 ° C. for 60 minutes. The solution was changed from yellow to brown, and the reaction was continued at 80 ° C. for 60 minutes. Stirring is stopped and solid disappears. (TLC is carried out in proportions of ethyl acetate: petroleum ether = 1: 8, and the reaction is stopped.) After standing overnight, washing with water, extracting the water phase, combining the organic phase, drying and spin- ) And then dispersed in dichloromethane to obtain 15 g of a white solid which was recrystallized from toluene / dichloromethane to give 12.3 g of a white solid compound M56, the yield of the last two steps being 45%.

Example 57

Synthesis of compound M57

The structural formula and the synthesis route of the compound M57 prepared in this Example are as follows.

A similar method to Example 56 was used, replacing p-diphenylamine phenylboronic acid with the same equivalent of 4-carbazole phenyl-boronic acid to give compound M57 (white solid, yield 52%).

Example 58

Synthesis of compound M58

The structural formula and the synthesis route of the compound M58 prepared in this Example are as follows.

A similar procedure to that of Example 56 was used, replacing p-diphenylamine phenylboronic acid with the same equivalent of 9-phenyl-9H-carbazole-3-boric acid to give compound M58 (white solid, yield 43%).

Example 59

Synthesis of compound M59

The structural formula and the synthesis route of the compound M59 prepared in this Example are as follows.

(1) Synthesis of intermediate M59-1

To a three-neck flask equipped with a condenser tube under the protection of nitrogen gas, 21.3 g (100 mmol) of 3-bromobenzothiophene, 18.3 g (22 mmol) of carbazole, 14.4 g (150 mmol) of sodium tert-butoxide and 300 ml of toluene , Then 20.54 g of Pd (dba) and 34 ml of 10% P (t-Bu) were added and the reaction mixture was heated to reflux reaction for 10 hours, then cooled and water was added to quench the reaction, After extracting with ethyl acetate twice, the organic phase was combined, dried over anhydrous magnesium sulfate, and swab-off until the solvent was dried to obtain a yellow oily substance. Petroleum ether was added thereto to shake the solid until precipitation The resulting solid was filtered, washed with methyl alcohol and petroleum ether, and dried to obtain 19.4 g of a white solid M56-1 with a yield of 65%.

(2) Synthesis of M59

A. To a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas, 30 g (100 mmol) of M59-1 and 500 ml of dried THF were added, cooled to -78 ° C and 50 ml (120 mmol) of 2.4 M n- After the solution turned from yellowish brown to dark black, the reaction was maintained at -60 ° C. for 30 minutes, cooled to -78 ° C., and 30 g (159.5 mmol) of triisopropyl borate was added dropwise. The solution was then allowed to warm to room temperature, . After saturated aqueous ammonium chloride solution was added for cancellation, the mixture was stirred for 30 minutes and separated. The aqueous phase was extracted, and the organic phase was combined, dried with anhydrous magnesium sulfate, dispersed with petroleum ether, and subjected to ultrasonic treatment. To obtain a white solid, which is then used directly in the next step of the reaction.

B. In a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, 9.6 g (20 mmol) of the above-prepared starting material (100 mmol), tri- (p-bromophenyl) amine, 1.2 g of tetrakistriphenylphosphine palladium , 300 ml of toluene, 120 ml of ethyl alcohol, 52 g of sodium carbonate and 200 ml of water were added and the mixture was reacted at 70 ° C. for 60 minutes. The solution was changed from yellow to brown, and the reaction was continued at 80 ° C. for 60 minutes. Stirring is stopped and solid disappears. (TLC is carried out in proportions of ethyl acetate: petroleum ether = 1: 8, and the reaction is stopped.) After standing overnight, washing with water, extracting the water phase, combining the organic phase, drying and spin- ), Followed by dispersion in dichloromethane to obtain 15 g of a white solid, which was then recrystallized from toluene / dichloromethane to obtain 11.4 g of a white solid compound M59, the yield of the last two steps being 50%.

Example 60

Synthesis of compound M60

The structure and the synthesis route of the compound M60 prepared in this Example are as follows.

After 2,3-dibromobenzothiophene and 4- (diphenylamino) phenylboric acid were subjected to Suzuki coupling reaction to obtain intermediate M60-1, an intermediate M60-2 was obtained according to a conventional method for preparing boric acid. After the Suzuki coupling reaction with 3,3'-dibromo-2,2'-bibenzo (b) thiophene, intermediate M60-3 was obtained, followed by N-phenylcarbazole-3-boric acid and Suzuki coupling group Compound M60 was obtained (white solid, yield 33%).

Example 61

Synthesis of Compound M61

The structural formula and the synthesis route of the compound M61 prepared in this Example are as follows.

The synthesis method is analogous to Example 60 and in the third step, the intermediate M61-1 (see synthesis of the Journal of the Chemical Society, 1942, p. 404 and 412) was used to synthesize 3,3'-dibromo-2,2'- (b) thiophene to give compound M61 (white solid, yield 18%).

Example 62

Synthesis of Compound M62

The structure and the synthesis route of the compound M62 prepared in this Example are as follows.

A similar method to Example 64 was used, replacing the same equivalent of 3-boric acid-N-methylcarbazole with 3-boric acid-N-phenylcarbazole and obtaining compound M62 (white solid, yield 56%).

Example 63

Synthesis of compound M63

The structure and the synthesis route of the compound M63 prepared in this Example are as follows.

Benzothiophene was reacted with n-butyllithium to obtain a lithium salt, followed by homocoupling reaction under the action of anhydrous copper chloride to obtain intermediate M63-1, followed by NBS bromination to give homobromide M63-2 And reacted with n-butyllithium to form a lithium salt. Under the action of anhydrous copper chloride, the intermediate M63-3 was obtained through a homo-coupling reaction, and then subjected to NBS-bromination to obtain a polybromide M63-4. -3-boronic acid and Suzuki coupling reaction to give compound M63 (white solid, yield 53%).

Example 64

Synthesis of compound M64

The structure and the synthesis route of the compound M64 prepared in this Example are as follows.

(1) Synthesis of M64-1

(121.91 mmol) of 3-boric acid-N-phenylcarbazole, 23 g of 3-bromobenzothiophene, 3.5 g of tetrakis (triphenylphosphine) palladium, 250 ml of toluene, 100 ml of ethyl alcohol and 140 ml of water / 200 ml of water were added and reacted at 80 ° C. for 40 minutes. The reaction was terminated by TLC. When the result was complete reaction, the reaction was stopped, cooled to room temperature, The water phase was extracted, the organic phase was combined, dried and spin-dried to obtain a yellow oily substance. Column chromatography (dichloromethane / petroleum ether) was carried out to obtain 30 g of a white solid.

(2) Synthesis of M64

A. To a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection, 25 g (66.65 mmol) of M64-1 and 500 ml of dried THF were added, cooled to -78 ° C and 50 ml (120 mmol) of 2.4 M n- After the solution was changed from yellowish brown to dark black, the solution was maintained at -60 ° C. to -20 ° C., followed by maintaining the temperature for 120 minutes, cooling to -78 ° C., dropping 30 g (159.5 mmol) of triisopropyl borate, It is changed from emerald color to yellow color and stirred overnight. And the mixture was stirred for 30 minutes. The aqueous phase was extracted, and the organic phase was combined. The organic phase was dried, dried over anhydrous magnesium sulfate, dispersed with petroleum ether, sonicated, and filtered to remove pale yellow After obtaining the oily substance, it is directly used for the next step reaction.

B. In a 1000 ml three-necked flask equipped with a mechanical stirrer under nitrogen gas protection were added the above prepared feed (46.65 mmol), 8.4 g of 3,3'-dibromo-2,2'-bibenzo (b) thiophene 1.2 g of tetrakistriphenylphosphine palladium, 300 ml of toluene, 120 ml of ethyl alcohol, 52 g of sodium carbonate and 200 ml of water were charged and reacted at 70 ° C. for 60 minutes. Then, the solution was changed from yellow to brown at 80 ° C. for 60 minutes Upon reaction and stirring, the presence of solid granules is observed, stirring is stopped, and the solid disappears. (TLC is carried out in proportions of ethyl acetate: petroleum ether = 1: 8, and the reaction is stopped.) After standing overnight, washing with water, extracting the water phase, combining the organic phase, drying and spin- ) To obtain 15 g of a white solid which was recrystallized from toluene / dichloromethane to give 9.1 g of white solid M3. The yield of the last two steps was 45%.

Example 65

Synthesis of compound M65

The structural formula and the synthesis route of the compound M65 prepared in this Example are as follows.

(1) Nitrogen gas protection, 500 ml three-necked flask, DCM (200 mL) containing dissolved M65-1 (5.62 g, 10 mmol, 1 eq) (Tetrahedron 1986, V42 (2), P763-773) at room temperature and magnetic stirring ) Was added Et3N (4.04 g, 40 mmol, 2 eq) in one portion. After the addition, the system gradually turned purple and stirred continuously at room temperature for 30 minutes. Tf2O (8.46 g, 30 mmol, 1.5 eq) was added dropwise to the system. Lt; / RTI > The reaction was stopped by addition of water (100 ml) when the result of the reaction was observed by TLC and the raw material was completely reacted. The aqueous phase is extracted with DCM (50 ml). The combined organic phases were washed with saturated brine (100 ml), dried over anhydrous magnesium sulfate and filtered. After drying under reduced pressure (spin drying), a brown oily substance was obtained. After dissolving in DCM, the sample is stirred with silica gel and loaded by dry method. After eluting with PE / EtOAc = 30: 1, the product was spin-dried under reduced pressure to obtain 5 g of a white solid. The yield was 60%.

(2 g), M65-2 (5 g, 6 mmol, 1 eq), 4- (diphenylamino) phenylboric acid (2.17 g, 14.47 mmol, 1.2 eq), Na2CO3 Pd (PPh3) 4 (468 mg, 0.41 mmol) was added to a suspension of toluene / EtOH / H2O (50 ml / 50 ml / 50 ml) in which KBr (49 mg, 0.41 mmol, 5% eq) , 5% eq). After heating to reflux and warming and reacting for 3 hours (the system gradually evolves from the suspension as the retention time is extended), the pressure is reduced when the TLC results are complete, and the solvent is spin-dried ), Dissolved in EtOAc (150 ml), washed with water (80 ml) and the aqueous phase extracted with EtOAc (50 ml). The combined organic phases were washed with saturated brine (100 ml), dried over anhydrous magnesium sulfate and filtered. The oil phase was obtained by spin drying under reduced pressure. After dissolving in DCM, the sample is stirred with silica gel. Separation by column chromatography yielded 4.6 g of a white solid with a yield of 75%.

The following are mass spectrum and elemental analysis data of the compound M1-M65 of the present invention.

M1 The product MS (m / e): 748, elemental analysis (C ₅₂ H ₃₂ N ₂ S ₂ ): theoretical value C: 83.39%, H: 4.31%, N: 3.74%, S: 8.56% %, H: 4.31%, N: 3.74%, S: 8.57% M2 The product MS (m / e): 748, elemental analysis (C ₅₂ H ₃₂ N ₂ S ₂ ): theoretical value C: 83.39%, H: 4.31%, N: 3.74%, S: 8.56% %, H: 4.31%, N: 3.73%, S: 8.59% M3 Product MS (m / e): 752 , Elemental analysis _{(C 52 H 36 N 2 S} 2): theoretical value C: 82.94%, H: 4.82 %, N: 3.72%, S: 8.52%, measured value C: 82.98 %, H: 4.81%, N: 3.71%, S: 8.50% M4 Product MS (m / e): 764 , Elemental analysis _{(C 53 H 36 N 2 S} 2): theoretical value C: 83.21%, H: 4.74 %, N: 3.66%, S: 8.38%, measured value C: 83.21 %, H: 4.73%, N: 3.67%, S: 8.38% M5 Product MS (m / e): 848 , Elemental analysis _{(C 60 H 36 N 2 S} 2): theoretical value C: 84.87%, H: 4.27 %, N: 3.30%, S: 7.55%, measured value C: 84.87 %, H: 4.27%, N: 3.30%, S: 7.55% M6 H: 4.27%, N: 3.30%, S: 7.55%, measured value C: 84.90 (calculated as C: 84.87%, MS: m / e): 848, elemental analysis (C ₆₀ H ₃₆ N ₂ S ₂ ) %, H: 4.26%, N: 3.29%, S: 7.54% M7 The product MS (m / e): 748, elemental analysis (C ₅₂ H ₃₂ N ₂ S ₂ ): theoretical value C: 83.39%, H: 4.31%, N: 3.74%, S: 8.56% %, H: 4.35%, N: 3.72%, S: 8.58% M8 Product MS (m / e): 752 , Elemental analysis _{(C 52 H 36 N 2 S} 2): theoretical value C: 82.94%, H: 4.82 %, N: 3.72%, S: 8.52%, measured value C: 82.93 %, H: 4.82%, N: 3.72%, S: 8.53% M9 H: 4.27%, N: 3.30%, S: 7.55%, measured value C: 84.84%, and the product C (m / e): 848, elemental analysis (C ₆₀ H ₃₆ N ₂ S ₂ ) %, H: 4.29%, N: 3.30%, S: 7.56% M10 Product MS (m / e): 690 , Elemental analysis _{(C 47 H 34 N 2 S} 2): theoretical value C: 81.70%, H: 4.96 %, N: 4.05%, S: 9.28%, measured value C: 81.73 %, H: 4.95%, N: 4.04%, S: 9.28% M11 Product MS (m / e): 776 , Elemental analysis _{(C 54 H 36 N 2 S} 2): theoretical value C: 83.47%, H: 4.67 %, N: 3.61%, S: 8.25%, measured value C: 83.45 %, H: 4.68%, N: 3.61%, S: 8.26% M12 Product MS (m / e): 767 , Elemental analysis _{(C 52 H 3 NS 3)} : theoretical value C: 81.32%, H: 4.33 %, N: 1.82%, S: 12.53%, measured value C: 81.30%, H: 4.33%, N: 1.82%, S: 12.55% M13 The product MS (m / e): 748, elemental analysis (C ₅₂ H ₃₂ N ₂ S ₂ ): theoretical value C: 83.39%, H: 4.31%, N: 3.74%, S: 8.56% %, H: 4.30%, N: 3.73%, S: 8.58% M14 Product MS (m / e): 630 , Elemental analysis _{(C 40 H 22 S 4)} : theoretical value C: 76.15%, H: 3.51 %, S: 20.33%, measured value C: 76.17%, H: 4.50 %, S: 20.32% M15 Product MS (m / e): 682 , Elemental analysis _{(C 44 H 26 S 4)} : theoretical value C: 77.38%, H: 3.84 %, S: 18.78%, measured value C: 77.35%, H: 4.85 %, S: 18.80% M16 Product MS (m / e): 782 , Elemental analysis _{(C 52 H 30 S 4)} : theoretical value C: 79.76%, H: 3.86 %, S: 16.38%, measured value C: 79.78%, H: 3.86 %, S: 16.36% M17 MS: m / e: 630, elemental analysis (C ₄₀ H ₂₂ S ₄ ): theoretical values C: 76.15%, H: 3.51%, S: 20.33%, C: 76.15% S: 20.34% M18 Product MS (m / e): 630 , Elemental analysis _{(C 40 H 22 S 4)} : theoretical value C: 76.15%, H: 3.51 %, S: 20.33%, measured value C: 76.15%, H: 3.51 %, S: 20.33% M19 The product MS (m / e): 598, elemental analysis (C ₄₀ H ₂₂ O ₂ S ₂ ): theoretical value C: 80.24%, H: 3.70%, O: 5.34%, S: 10.71% %, H: 3.71%, O: 5.35%, S: 10.73% M20 Product MS (m / e): 598 , Elemental analysis _{(C 40 H 22 O 2 S} 2): theoretical value C: 80.24%, H: 3.70 %, O: 5.34%, S: 10.71%, measured value C: 80.26 %, H: 3.70%, O: 5.33%, S: 10.70% M21 Product MS (m / e): 904 , Elemental analysis _{(C 64 H 44 N 2 S} 2): theoretical value C: 84.92%, H: 4.90 %, N: 3.09%, S: 7.08%, measured value C: 84.90 %, H: 4.91%, N: 3.09%, S: 7.09% M22 H: 4.22%, N: 3.66%, O: 2.09%, S: 8.38%, S: m / e: 764, elemental analysis (C ₅₂ H ₃₂ N ₂ OS ₂ ) Measured values C: 81.63%, H: 4.23%, N: 3.66%, O: 2.10%, S: 8.38% M23 H: 4.22%, N: 3.66%, O: 2.09%, S: 8.38%, S: m / e: 764, elemental analysis (C ₅₂ H ₃₂ N ₂ OS ₂ ) Measured values C: 81.65%, H: 4.22%, N: 3.66%, O: 2.09%, S: 8.38% M24 H: 4.72%, N: 3.64%, O: 2.08%, S: 8.34%, S: m / e: 768, elemental analysis (C ₅₂ H ₃₆ N ₂ OS ₂ ) Measured values C: 81.23%, H: 4.73%, N: 3.63%, O: 2.07%, S: 8.34% M25 H: 4.22%, N: 3.66%, O: 2.09%, S: 8.38%, S: m / e: 764, elemental analysis (C ₅₂ H ₃₂ N ₂ OS ₂ ) Measured values C: 81.65%, H: 4.23%, N: 3.67%, O: 2.08%, S: 8.37% M26 79.56%, H: 4.62%, N: 3.57%, S: 12.25%, measured value C: 79.50 (M / e): 784, elemental analysis (C ₅₂ H ₃₆ N ₂ S ₃ ) %, H: 4.60%, N: 3.61%, S: 12.29% M27 The product MS (m / e): 780, elemental analysis (C ₅₂ H ₃₂ N ₂ S ₃ ): theoretical value C: 79.97%, H: 4.13%, N: 3.59%, S: 12.55% %, H: 4.13%, N: 3.59%, S: 12.54% M28 82.53%, H: 4.90%, N: 4.98%, S: 7.60%, measured value C: 82.54 (M / e): 843, Elemental analysis (C ₅₈ H ₄₁ N ₃ S ₂ ) %, H: 4.90%, N: 4.96%, S: 7.61% M29 H: 4.44%, N: 5.00%, S: 7.63%, Measured value C: 82.90 (calculated as C: 82.92%, MS: m / e): 839, elemental analysis (C ₅₈ H ₃₇ N ₃ S ₂ ) %, H: 4.43%, N: 5.01%, S: 7.65% M30 H: 4.44%, N: 5.00%, S: 7.63%, measured value C: 82.92%, and the product C (m / e): 839, elemental analysis (C ₅₈ H ₃₇ N ₃ S ₂ ) %, H: 4.44%, N: 5.00%, S: 7.63% M31 Product MS (m / e): 839 , Elemental analysis _{(C 58 H 37 N 3 S} 2): theoretical value C: 82.92%, H: 4.44 %, N: 5.00%, S: 7.63%, measured value C: 82.91 %, H: 4.44%, N: 5.01%, S: 7.63% M32 Product MS (m / e): 721 , Elemental analysis _{(C 46 H 27 NS 4)} : theoretical value C: 76.53%, H: 3.77 %, N: 1.94%, S: 17.77%, measured value C: 76.50%, H: 3.78%, N: 1.95%, S: 17.78% M33 Product MS (m / e): 689 , Elemental analysis _{(C 46 H 27 NO 2 S} 2): theoretical value C: 80.09%, H: 3.95 %, N: 2.03%, O: 4.64%, S: 9.30%, Measured values C: 80.10%, H: 3.94%, N: 2.04, O: 4.63%, S: 9.30% M34 Product MS (m / e): 773 , Elemental analysis _{(C 50 H 31 NS 4)} : theoretical value C: 77.58%, H: 4.04 %, N: 1.81%, S: 16.57%, measured value C: 77.55%, H: 4.05%, N: 1.82%, S: 16.58% M35 H: 4.40%, N: 3.05%, O: 1.74%, S: 6.99%, S: m / e: 916, elemental analysis (C ₆₄ H ₄₀ N ₂ OS ₂ ) Measured values C: 83.79%, H: 4.39%, N: 3.06, O: 1.75%, S: 7.00% M36 H: 4.40%, N: 3.05%, O: 1.74%, S: 6.99%, S: m / e: 916, elemental analysis (C ₆₄ H ₄₀ N ₂ OS ₂ ) Measured values C: 83.81%, H: 4.40%, N: 3.05, O: 1.74%, S: 6.99% M37 H: 4.81%, N: 3.04%, O: 1.74%, S: 6.96%, S: m / e: 920, elemental analysis (C ₆₄ H ₄₄ N ₂ OS ₂ ) Measured values C: 83.46%, H: 4.81%, N: 3.04, O: 1.74%, S: 6.95% M38 H: 4.40%, N: 3.05%, O: 1.74%, S: 6.99%, S: m / e: 916, elemental analysis (C ₆₄ H ₄₀ N ₂ OS ₂ ) Measured values C: 3.81%, H: 4.40%, N: 3.05, O: 1.74%, S: 6.99% M39 The product MS (m / e): 930, elemental analysis C ₆₄ H ₃₈ N ₂ S ₃ : theoretical value C: 82.55%, H: 4.11%, N: 3.01%, S: 10.33% %, H: 4.12%, N: 3.02, S: 10.33% M40 The product MS (m / e): 934, elemental analysis (C ₆₄ H ₄₂ N ₂ S ₃ ): theoretical value C: 82.19%, H: 4.53%, N: 3.00%, S: 10.29% %, H: 4.52%, N: 3.04, S: 10.32% M41 The product MS (m / e): 930, elemental analysis (C ₆₄ H ₃₈ N ₂ S ₃ ): theoretical value C: 82.55%, H: 4.11%, N: 3.01%, S: 10.33% %, H: 4.10%, N: 3.00, S: 10.32% M42 The product MS (m / e): 934, elemental analysis (C ₆₄ H ₄₂ N ₂ S ₃ ): theoretical value C: 82.19%, H: 4.53%, N: 3.00%, S: 10.29% %, H: 4.53%, N: 3.00, S: 10.29% M43 The product MS (m / e): 930, elemental analysis (C ₆₄ H ₃₈ N ₂ S ₃ ): theoretical value C: 82.55%, H: 4.11%, N: 3.01%, S: 10.33% %, H: 4.12%, N: 3.01, S: 10.35% M44 Product MS (m / e): 914 , Elemental analysis _{(C 64 H 38 N 2 OS} 2): theoretical value C: 84.00%, H: 4.19 %, N: 3.06%, O: 1.75%, S: 7.01%, Measured value C: 84.03%, H: 4.19%, N: 3.06%, O: 1.75% S: 6.08% M45 H: 4.61%, N: 3.05%, O: 1.74%, S: 6.98%, S: m / e: 918, elemental analysis (C ₆₄ H ₄₂ N ₂ OS ₂ ) Measured values C: 83.60%, H: 4.61%, N: 3.05%, O: 1.74% S: 7.01% M46 Product MS (m / e): 914 , Elemental analysis _{(C 64 H 38 N 2 OS} 2): theoretical value C: 84.00%, H: 4.19 %, N: 3.06%, O: 1.75%, S: 7.01%, Measurement value C: 84.00%, H: 4.19%, N: 3.06%, O: 1.75% S: 7.01% M47 Product MS (m / e): 1019 , Elemental analysis _{(C 72 H 49 N 3 S} 2): theoretical value C: 84.76%, H: 4.84 %, N: 4.12%, S: 6.29%, measured value C: 84.75 %, H: 4.84%, N: 4.12%, S: 6.30% M48 Product MS (m / e): 995 , Elemental analysis _{(C 70 H 49 N 3 S} 2): theoretical value C: 84.39%, H: 4.96 %, N: 4.22%, S: 6.44%, measured value C: 84.40 %, H: 4.95%, N: 4.22%, S: 6.44% M49 Product MS (m / e): 925 , Elemental analysis _{(C 62 H 39 NS 4)} : theoretical value C: 80.40%, H: 4.24 %, N: 1.51%, S: 13.85%, measured value C: 80.38%, H: 4.25%, N: 1.51%, S: 13.86% M50 Product MS (m / e): 873 , Elemental analysis _{(C 58 H 35 NS 4)} : theoretical value C: 79.69%, H: 4.04 %, N: 1.60%, S: 14.67%, measured value C: 79.70%, H: 4.04%, N: 1.60%, S: 14.66% M51 Product MS (m / e): 989 , Elemental analysis _{(C 70 H 43 N 3 S} 2): theoretical value C: 84.90%, H: 4.38 %, N: 4.24%, S: 6.48%, measured value C: 84.90 %, H: 4.38%, N: 4.24%, S: 6.48% M52 The product MS (m / e): 989, elemental analysis (C ₇₀ H ₄₃ N ₃ S ₂ ): theoretical value C: 84.90%, H: 4.38%, N: 4.24%, S: 6.48% %, H: 4.37%, N: 4.23%, S: 6.49% M53 Product MS (m / e): 989 , Elemental analysis _{(C 70 H 43 N 3 S} 2): theoretical value C: 84.90%, H: 4.38 %, N: 4.24%, S: 6.48%, measured value C: 84.88 %, H: 4.39%, N: 4.24%, S: 6.49% M54 Product MS (m / e): 1041 , Elemental analysis _{(C 74 H 47 N 3 S} 2): theoretical value C: 85.27%, H: 4.54 %, N: 4.03%, S: 6.15%, measured value C: 85.28 %, H: 4.53%, N: 4.03%, S: 6.15% M55 H: 4.73%, N: 4.53%, S: 5.19%, Measured value C: 85.55 (mass%). MS: m / e: 1234, elemental analysis (C ₈₈ H ₅₈ N ₄ S ₂ ) %, H: 4.73%, N: 4.53%, S: 5.18% M56 H: 4.85%, N: 4.08%, S: 7.01%, Measured value C: 84.04 (mass%). MS: m / e: 1370, elemental analysis (C ₉₆ H ₆₆ N ₄ S ₃ ) %, H: 4.86%, N: 4.08%, S: 7.01% M57 The product C (84.43%), H (4.43%), N (4.10%), S (7.04%), C (84.47%), MS (m / e): 1364, elemental analysis (C ₉₆ H ₆₀ N ₄ S ₃ ) %, H: 4.42%, N: 4.09%, S: 7.02% M58 The product C (84.43%), H (4.43%), N (4.10%), S (7.04%), C (84.45%), MS (m / e): 1364, elemental analysis (C ₉₆ H ₆₀ N ₄ S ₃ ) %, H: 4.43%, N: 4.10%, S: 7.02% M59 H: 4.23%, N: 4.93%, S: 8.46%, Measured value C: 82.38 (calculated value). MS: m / e: 1136 Elemental analysis (C ₇₈ H ₄₈ N ₄ S ₃ ) %, H: 4.25%, N: 4.93%, S: 8.44% M60 Product MS (m / e): 882 , Elemental analysis _{(C 60 H 38 N 2 S} 3): theoretical value C: 81.60%, H: 4.34 %, N: 3.17%, S: 10.89%, measured value C: 81.62 %, H: 4.33%, N: 3.17%, S: 10.88 M61 H (4.32%), N (3.00%), S (10.31%), C (82.39%), MS (m / e): 932, elemental analysis (C ₆₄ H ₄₀ N ₂ S ₃ ) %, H: 4.31%, N: 3.00%, S: 10.30% M62 The product MS (m / e): 888, elemental analysis (C ₅₈ H ₃₆ N ₂ S ₄ ): theoretical value C: 78.34%, H: 4.08%, N: 3.15%, S: 14.42% %, H: 4.08%, N: 3.14%, S: 14.43% M63 The product MS (m / e): 888, elemental analysis (C ₅₈ H ₃₆ N ₂ S ₄ ): theoretical value C: 78.34%, H: 4.08%, N: 3.15%, S: 14.42% %, H: 4.07%, N: 3.14%, S: 14.40% M64 Product MS (m / e): 1012 , Elemental analysis _{(C 68 H 40 N 2 S} 4): theoretical value C: 80.60%, H: 3.98 %, N: 2.76%, S: 12.66%, measured value C: 80.55 %, H: 3.99%, N: 2.77%, S: 12.69% M65 The product MS (m / e): 1016, elemental analysis (C ₆₈ H ₄₄ N ₂ S ₄ ): theoretical value C: 80.28%, H: 4.36%, N: 2.75%, S: 12.61% %, H: 4.36%, N: 2.75%, S: 12.62%

In order to further understand the technical solution in the present application, it is necessary to explain that a conventional organic electroluminescent device is composed of a substrate, a cathode, an organic light emitting functional layer and a cathode, , A hole transport layer, an organic emission layer, an electron transport layer, and an electron injection layer.

The material used for the hole injection layer is a hole injecting material, the material used for the hole transporting layer is a hole transporting material, the material used for the organic light emitting layer is an organic light emitting material, the organic light emitting material includes a main material and a doping dye, It is an electron transfer material. Similarly, an electron injection material is used for the electron injection layer. In particular, in the application of the organic electroluminescent device, the main material of the organic light emitting layer may be a binary material composed of one or two materials.

Example 66

Application examples of the compound of the present invention

In order to compare the performance of such a hole injection or hole transport material, a series of simple electroluminescent devices are designed in the present invention. As a contrast material of the hole injecting material, the hole injection layer material 2-TNATA commonly used in the prior art was used. As the contrast material of the hole transporting material, the hole transporting material NPB commonly used in the prior art was used and the ADN doping TBPe was used as the organic light emitting layer (AND is the address material and TBPe is the light emitting material).

The structure of the organic electroluminescent device in the embodiment of the present invention is the same as that of the conventional organic light emitting diode (OLED), which is a substrate / anode / hole injection layer (HIL) / hole transport layer (HTL) / organic light emitting layer (EL) / electron transport layer Can be used as a substrate, for example, glass or plastic. When the organic electroluminescent device of the present invention is manufactured, a glass substrate is selected and ITO is used as a cathode material.

In the hole injecting material, the material of the present invention is used in Examples, and 2-TNATA is used in Comparative Examples.

In the hole transporting layer, the material of the present invention is used in Examples, and NPB is used in Comparative Examples.

As the light emitting layer, blue light-based ADN-doped blue light dye TBPe was used.

As the electron transport layer, an electron transport material BPhen commonly used in the prior art was used.

The cathode may be made of a metal and a mixture thereof, and may be, for example, Mg, Ag, Ca: Ag or the like, and may have an electron injection layer / metal layer structure. For example, LiF / Al, Li ₂ O / . The cathode material used in the manufacturing process of the organic electroluminescent device of the present invention is LiF / Al.

Example 67

The compound in this example was used as an electron transfer material in an organic electroluminescent device, and ADN-doped blue light dye TBPe was used as a material for a light emitting layer, and a plurality of organic electroluminescent devices were manufactured. The device structure is composed of ITO / hole injection material (60 nm) / hole transport material (20 nm) / AND: 5% wt TBPe (30 nm) BPhen (20 nm) / LiF (0.5 nm) / Al M5, M56, M60 and M65 are used as the hole-transporting material, and M1, M5, M10, M17, M20, M24, M25, M27, M29, M33, M35, M41, M48, M49, M51, .

The manufacturing process of the organic electroluminescent device in this embodiment is as follows.

The glass substrate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, washed with deionized water, sonicated in a mixed solvent of acetone and ethyl alcohol to remove oil, and then, when the water was completely removed in a clean environment And then the surface is impacted with a low energy ion beam while washing with ultraviolet rays and ozone.

A glass substrate having the positive electrode is placed in a vacuum chamber, and vacuum is removed from 1 x 10 ^-5 to 9 x 10 ^-3 Pa; The positive hole injection layer was vacuum-deposited on the positive electrode layer film at a deposition rate of 0.1 nm / s and a deposited film thickness of 60 nm. The materials used in this layer are different depending on the embodiment, and specifically, refer to the embodiment section.

The hole transport layer was vacuum deposited on the hole injection layer film, and the deposition rate was 0.1 nm / s. The thickness of the deposited film was 20 nm.

The deposition rate of ADN was 0.1 nm / s, the deposition rate of TBPe was 0.005 nm / s, and the total thickness of the deposited films Is 30 nm.

BPhen is vacuum-deposited on the light-emitting layer to form an electron transfer layer of an organic electric field device. The deposition rate thereof is 0.1 nm / s, and the total thickness of the deposited film is 20 nm.

0.5 nm of LiF was vacuum deposited on the electron transport layer (ETL) to form an electron injection layer, and Al of 150 nm was used as the cathode of the device.

The manufacturing method of the comparative example was the same as that of the example, and only the compound as the hole injecting element or the hole transmitting element was changed.

The performance of the organic electroluminescent device is shown in the following table.

Element number Hole injection material Hole transport material Required luminance Cd / m ² Voltage V Current efficiency cd / A Comparative Example 1 2-TNATA NPB 1000 5.9 6.0 OLED1 M1 M5 1000 5.3 6.8 OLED2 M2 M10 1000 5.1 6.7 OLED3 M3 M17 1000 5.0 7.0 OLED4 M4 M20 1000 5.7 7.2 OLED5 M5 M24 1000 5.4 7.1 OLED6 M6 M25 1000 5.5 7.0 OLED7 M7 M27 1000 5.2 6.9 OLED8 M8 M29 1000 5.5 6.8 OLED9 M9 M33 1000 4.9 7.3 OLED10 M10 M35 1000 5.4 7.2 OLED11 M11 M41 1000 5.0 6.8 OLED12 M12 M48 1000 5.3 7.1 OLED13 M13 M49 1000 5.4 6.6 OLED14 M14 M51 1000 5.1 6.4 OLED15 M15 M56 1000 4.9 6.7 OLED16 M16 M60 1000 5.4 6.9 OLED17 M17 M65 1000 5.3 6.6 OLED18 M18 NPB 1000 5.0 6.7 OLED19 M19 NPB 1000 5.1 7.0 OLED20 M20 NPB 1000 5.6 6.8 OLED21 M21 NPB 1000 5.4 6.5 OLED22 M22 NPB 1000 5.5 6.8 OLED23 M23 NPB 1000 5.2 6.7 OLED24 M24 NPB 1000 5.3 6.6 OLED25 M25 NPB 1000 5.5 6.8 OLED26 M26 NPB 1000 5.6 6.6 OLED27 M27 NPB 1000 5.4 6.4 OLED28 M28 NPB 1000 5.3 6.8 OLED29 M29 NPB 1000 5.1 6.9 OLED30 M30 NPB 1000 5.5 6.7 OLED31 M31 NPB 1000 5.6 6.8 OLED32 M32 NPB 1000 5.4 6.9 OLED33 M33 NPB 1000 5.2 6.6 OLED34 M34 NPB 1000 5.5 6.4 OLED35 M35 NPB 1000 5.2 6.7 OLED36 M36 NPB 1000 4.9 6.5 OLED37 M37 NPB 1000 5.1 6.4 OLED38 M38 NPB 1000 5.4 6.5 OLED39 M39 NPB 1000 5.0 6.8 OLED40 M40 NPB 1000 5.7 6.3 OLED41 M41 NPB 1000 5.1 6.9 OLED42 M42 NPB 1000 5.3 6.8 OLED43 M43 NPB 1000 5.2 6.7 OLED44 M44 NPB 1000 5.4 6.9 OLED45 M45 NPB 1000 5.1 6.3 OLED46 M46 NPB 1000 5.5 6.7 OLED47 M47 NPB 1000 5.6 6.5 OLED48 M48 NPB 1000 5.5 6.7 OLED49 M49 NPB 1000 5.3 6.9 OLED50 M50 NPB 1000 5.4 6.6 OLED51 M51 NPB 1000 5.5 6.9 OLED52 M52 NPB 1000 5.4 7.0 OLED53 M53 NPB 1000 5.2 6.6 OLED54 M54 NPB 1000 5.5 6.5 OLED55 M55 NPB 1000 5.2 6.7 OLED 56 M56 NPB 1000 5.1 6.7 OLED57 M57 NPB 1000 5.5 6.6 OLED58 M58 NPB 1000 5.0 6.6 OLED59 M59 NPB 1000 5.4 6.8 OLED60 M60 NPB 1000 5.5 6.7 OLED61 M61 NPB 1000 4.9 7.0 OLED62 M62 NPB 1000 5.3 7.1 OLED63 M63 NPB 1000 5.4 7.2 OLED64 M64 NPB 1000 5.2 7.0 OLED65 M65 NPB 1000 5.1 6.9 OLED66 2-TNATA M1 1000 5.3 6.6 OLED67 2-TNATA M10 1000 5.1 6.4 OLED68 2-TNATA M17 1000 4.9 6.5 OLED69 2-TNATA M20 1000 5.5 6.8 OLED70 2-TNATA M24 1000 5.4 6.6 OLED71 2-TNATA M25 1000 5.2 7.0 OLED72 2-TNATA M27 1000 5.0 6.6 OLED73 2-TNATA M29 1000 5.3 6.7 OLED74 2-TNATA M33 1000 4.9 6.6 OLED75 2-TNATA M35 1000 4.8 7.1 OLED76 2-TNATA M41 1000 5.1 6.8 OLED77 2-TNATA M48 1000 5.2 6.6 OLED78 2-TNATA M49 1000 5.5 7.0 OLED79 2-TNATA M51 1000 5.0 6.8 OLED80 2-TNATA M56 1000 5.5 6.9

As can be seen from the above results, the OLED 1-OLED 17 used the novel organic material of the present invention as the hole injection layer material and the hole transport layer material of the organic electroluminescent device, respectively. As compared with Comparative Example 1, Can be improved. In the OLED18-OLED65, the novel organic material of the present invention was used as a hole injection layer material of an organic electroluminescent device and NPB was used as a hole transport material. OLED66 to OLED80, however, And 2-TNATA was used as the hole injection material. Compared with the comparative example 1, the device voltage reached 1v and the current efficiency of the device was remarkably increased. Since the novel organic material according to the present invention has a thiophene group, the lone pair of electrons on the S atom loses electrons and tends to form holes. Therefore, when the compound is used as a hole injecting and / or transferring material, a high charge carrier ) Have the ability to inject and deliver. Therefore, the luminous efficiency of the device can be greatly improved.

Example 68

Example 68 is an application example of the compound of the present invention.

The structure of the organic electroluminescent device in the embodiment of the present invention can be applied to a substrate, an anode / a hole injection layer (HIL) / a hole transport layer (HTL) / a subject: a fluorescent light emitting dye (EL) / an electron transport layer (ETL) Substrate / anode / hole injection layer (HIL) / hole transport layer (HTL) / first substance: second substance: a fluorescent light emitting dye (EL) / electron transport layer (ETL) / cathode.

A substrate in a conventional organic light emitting device can be used as a substrate, for example, glass or plastic. When the organic electroluminescent device of the present invention is manufactured, a glass substrate is selected and ITO is used as a cathode material.

As the hole injection material, the hole injection layer material 2-TNATA commonly used in the prior art is used.

The hole transport material uses the hole transporting material NPB which is commonly used in the prior art.

The electron transfer material uses Alq3, an electron transfer material commonly used in the prior art.

The cathode may be made of a metal and a mixture thereof, and may be, for example, Mg, Ag, Ca: Ag or the like, and may have an electron injection layer / metal layer structure. For example, LiF / Al, Li ₂ O / . The electron injecting material used in the manufacturing process of the device of the present invention is LiF and the cathode material is Al.

Example 69

The compound in this embodiment is used as one of the main materials or the pair of main materials in the organic electroluminescent device. (60 nm) / NPB (20 nm) / subject: blue light emitting dye (30 nm) Alq 3 (20 nm) / LiF (0.5 nm) / Al (150 nm) / ITO / 2-TNATA ). Or ITO / 2-TNATA (60 nm) / NPB (20 nm) / First subject: Second subject: Blue light emitting dye (30 nm) Alq3 (20 nm) / LiF (0.5 nm) / Al (150 nm)

The manufacturing process of the organic electroluminescent device in this embodiment is as follows.

The glass substrate coated with the ITO transparent conductive layer was ultrasonicated in a commercial cleaning agent, washed with deionized water, sonicated in a mixed solvent of acetone and ethyl alcohol to remove oil, and then completely removed in a clean environment And then the surface is impacted with a low energy cation beam while washing with ultraviolet rays and ozone.

A glass substrate having the positive electrode is placed in a vacuum chamber, and vacuum is removed to 1 x 10 ^-5 to 9 x 10 ^-3 Pa;

The positive hole injection layer was vacuum deposited on the anode layer film, and the deposition rate was 0.1 nm / s and the deposited film thickness was 60 nm

The hole transport layer was vacuum deposited on the hole injection layer film, and the deposition rate was 0.1 nm / s. The thickness of the deposited film was 20 nm.

The luminescent layer was vacuum deposited on the hole transport layer, and the main and luminescent dyes were deposited using co-deposition. The deposition rate of the subject was 0.1 nm / s, the deposition rate of the dye was 0.005 nm / s, and the total thickness of the deposited film was 30 nm . Alternatively, the first subject, the second subject, and the luminescent dye are deposited using a three-way co-deposition method, and the deposition rate of the first subject is 0.1 nm / s and the deposition rate of the second subject is varied according to each embodiment. See the example section. The deposition rate of the dye is 0.005 nm / s and the total thickness of the deposited film is 30 nm.

Particularly, the ratio in the parentheses in the light emitting layer structure of the OLEDs 104 to OLED 134 in the following table is a ratio of the deposition rate of the first main body to the main body.

Alq3 was vacuum deposited on the light emitting layer to form an electron transport layer of the device. The deposition rate thereof was 0.1 nm / s, and the total thickness of the deposited films was 20 nm.

LiF and Al were vacuum-deposited on the electron transport layer (ETL) to form a cathode of the device, and the thicknesses thereof were 0.5 nm and 150 nm, respectively. See the table below for the Zedium luminescent device.

Element number Hole injection material Required luminance Cd / m ² Voltage V Current efficiency cd / A Comparative Example 2 AND: TBPe 1000 6.0 5.8 OLED81 M1: TBPe 1000 5.7 6.5 OLED82 M5: TBPe 1000 5.5 6.4 OLED83 M10: TBPe 1000 5.4 6.7 OLED84 M13: TBPe 1000 5.0 7.3 OLED85 M17: TBPe 1000 5.1 7.0 OLED86 M20: TBPe 1000 4.9 7.2 OLED87 M24: TBPe 1000 4.8 7.4 OLED88 M25: TBPe 1000 5.0 7.2 OLED89 M27: TBPe 1000 4.9 7.5 OLED90 M29: TBPe 1000 5.0 7.3 OLED91 M33: TBPe 1000 5.3 7.1 OLED92 M35: TBPe 1000 4.9 6.8 OLED93 M41: TBPe 1000 4.9 6.6 OLED94 M47: TBPe 1000 5.0 7.1 OLED95 M48: TBPe 1000 5.1 6.7 OLED96 M49: TBPe 1000 5.1 6.8 OLED97 M51: TBPe 1000 5.0 7.2 OLED98 M53: TBPe 1000 5.0 7.5 OLED99 M56: TBPe 1000 4.8 6.9 OLED100 M57: TBPe 1000 4.7 6.9 OLED101 M59: TBPe 1000 5.2 7.2 OLED102 M60: TBPe 1000 4.9 7.5 OLED103 M65: TBPe 1000 5.2 7.5 OLED104 ADN: M47: TBPe (1: 0.05) 1000 5.5 6.8 OLED105 ADN: M47: TBPe (1: 0.2) 1000 5.2 7.5 OLED106 ADN: M47: TBPe (1: 0.8) 1000 5.1 7.3 OLED107 ADN: M47: TBPe (1: 1) 1000 5.0 7.2 OLED108 ADN: M47: TBPe (0.8: 1) 1000 5.1 7.0 OLED109 ADN: M47: TBPe (0.2: 1) 1000 5.3 6.9 OLED 110 ADN: M47: TBPe (0.05: 1) 1000 5.4 6.7 OLED111 ADN: M1: TBPe (1: 0.2) 1000 5.0 6.9 OLED 112 ADN: M5: TBPe (1: 0.2) 1000 4.9 7.3 OLED113 ADN: M10: TBPe (1: 0.2) 1000 4.9 7.6 OLED 114 ADN: M13: TBPe (1: 0.2) 1000 5.0 7.7 OLED115 ADN: M17: TBPe (1: 0.2) 1000 4.8 6.9 OLED116 ADN: M20: TBPe (1: 0.2) 1000 4.7 7.0 OLED117 ADN: M24: TBPe (1: 0.2) 1000 4.6 6.8 OLED118 ADN: M25: TBPe (1: 0.2) 1000 4.7 7.0 OLED119 ADN: M27: TBPe (1: 0.2) 1000 4.8 7.2 OLED 120 ADN: M29: TBPe (1: 0.2) 1000 4.9 7.5 OLED121 ADN: M33: TBPe (1: 0.2) 1000 4.9 7.2 OLED122 ADN: M35: TBPe (1: 0.2) 1000 4.7 7.0 OLED123 ADN: M41: TBPe (1: 0.2) 1000 5.1 7.4 OLED124 ADN: M48: TBPe (1: 0.2) 1000 5.0 7.2 OLED125 ADN: M49: TBPe (1: 0.2) 1000 4.9 6.9 OLED126 ADN: M51: TBPe (1: 0.2) 1000 4.8 6.8 OLED127 ADN: M53: TBPe (1: 0.2) 1000 5.2 7.7 OLED128 ADN: M56: TBPe (1: 0.2) 1000 5.3 7.9 OLED129 ADN: M59: TBPe (1: 0.2) 1000 5.1 7.8 OLED 130 ADN: M29: TBPe (1: 0.2) 1000 4.8 7.6 OLED131 ADN: M47: TBPe (1: 0.2) 1000 4.7 7.4 OLED132 ADN: M56: TBPe (1: 0.2) 1000 4.6 7.0 OLED133 ADN: M24: TBPe (1: 0.2) 1000 5.2 6.7 OLED134 ADN: M20: TBPe (1: 0.2) 1000 5.1 6.8

As can be seen from the data of the examples in the above table, the material of the present invention can be used as a main material for fluorescent blue light, and the material of the present invention can also be used as a twin main body in combination with other commercially available fluorescent blue light. The voltage of the device was lowered and the efficiency was improved as compared with Example 2.

Although the present invention has been described in connection with the above embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, the intention is to cover various modifications and improvements, Respectively.

Claims (11)

A benzothiophene derivative having a structure represented by the following formula (I), wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ -C ₄₀ arylamine group, a substituted or unsubstituted arylamine group, A substituted or unsubstituted benzothiophene group, a substituted or unsubstituted C ₄ to C ₄₀ carbazolyl group, a substituted or unsubstituted C ₄ to C ₄₀ benzothiophene group, a substituted or unsubstituted C ₄ to C ₄₀ benzofuranyl group,
L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,
R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &
m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3.

The benzothiophene derivative according to claim 1, wherein two adjacent groups in R ₃ -R ₁₀ are connected to form a ring to form one or more ring-opening structures. The method of claim 1, wherein R ₁ and R ₂ are independently selected from the group consisting of a C ₄ to C ₄₀ N-arylcarbazole group, a carbazolyl group, an N-alkylcarbazole group, a carbazole group, an alkyl group substituted carbazolyl group, Wherein the benzothiophene derivative is one selected from the group consisting of a benzoyl group, a diarylamine group, a benzothiophene group, a dibenzothiophene group, an aryl substituted benzothiophene group, a benzofuran group or a dibenzofurane group. The crosslinking group L of claim 1, wherein the crosslinking group L is a single bond, an N-alkylcarbazole group, a dibenzothiophene group, a dibenzofurane group, a triarylamine group, an N-arylcarbazole group, a substituted diphenyl ether, Diphenylsulfide. ≪ / RTI > The benzothiophene derivative according to claim 1, wherein the compound has the following structural formula.

The use of the benzothiophene derivative of claim 1 as a hole injecting material and / or a hole transmitting material in organic electroluminescent devices. The use of the benzothiophene derivative of claim 1 as an organic electroluminescent material as a main material in an organic electroluminescent device. 1. An organic electroluminescent device comprising a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer,
Wherein the material used for the organic emission functional layer includes a hole injection material, a hole transport material, an organic emission material, and an electron transfer material, and the material used for the organic emission functional layer has a compound represented by the following structural formula (I)

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group, a substituted or unsubstituted C ₄ -C ₄₀ benzofuran group,
L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,
R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &
m and n are selected from an integer of 0 to 3, and m + n is greater than 0 and less than or equal to 3. 1. An organic electroluminescent device comprising a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer,
Wherein the material used for the organic light emitting functional layer comprises a hole injection material, a hole transfer material, an organic light emitting material, and an electron transfer material, and the hole injection material has a compound represented by the following structural formula (I)

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group, a substituted or unsubstituted C ₄ -C ₄₀ benzofuran group,
L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,
R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &
m and n are selected from an integer of 0 to 3, and m + n is greater than 0 and less than or equal to 3. 1. An organic electroluminescent device comprising a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer,
Wherein the material used for the organic light emitting functional layer includes a hole injecting material, a hole transmitting material, an organic light emitting material, and an electron transmitting material, the hole transmitting material having a compound represented by the following structural formula (I)

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group, a substituted or unsubstituted C ₄ -C ₄₀ benzofuran group,
L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,
R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &
m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3. 1. An organic electroluminescent device comprising a substrate and an anode layer sequentially formed on the substrate, an organic light emitting functional layer and a cathode layer,
Wherein the material used for the organic light emitting functional layer includes a hole injection material, a hole transport material, an organic light emitting material, and an electron transfer material, and the main material of the organic light emitting material contains a compound represented by the following structural formula (I)

Wherein R ₁ and R ₂ are independently a substituted or unsubstituted C ₄ to C ₄₀ arylamine group, a substituted or unsubstituted C ₄ to C ₄₀ carbazole group, a substituted or unsubstituted C ₄ to C ₄₀ A benzothiophene group, a substituted or unsubstituted C ₄ -C ₄₀ benzofuran group,
L is a bridging group and a single bond, C ₄ ~ C ₄₀ substituted arylamine, C ₄ ~ C ₄₀ substituted carbazole, C ₄ ~ C ₄₀ substituted benzothiophene, an oxygen atom, a nitrogen atom or a sulfur in the Lt; / RTI > atoms,
R ₃ -R ₁₀ are independently selected from H atoms, C ₁ -C ₂₀ aliphatic linear or branched hydrocarbon groups, or C ₆ -C ₃₀ aromatic groups, and two adjacent groups are connected to form a ring to form a naphthothiophene derivative Lt; / RTI &
m and n are selected from integers of 0 to 3, and m + n is greater than 0 and less than or equal to 3.

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