CN107556229B - Preparation method of fluorenocarbazole organic electroluminescent material intermediate - Google Patents
Preparation method of fluorenocarbazole organic electroluminescent material intermediate Download PDFInfo
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Abstract
The invention relates to a preparation method of a fluorenocarbazole organic electroluminescent material intermediate, which comprises the steps of performing acetylation protection, nitration, deamination protection on an initial compound containing amino, converting the amino into a halogen substituent, and performing Suzuki coupling reaction and cyclization in sequence to obtain the fluorenocarbazole organic electroluminescent material intermediate. The invention has the advantages of high reaction selectivity and high yield; the reaction raw materials are cheap, and the preparation process is simple; and the reaction product is easy to be post-processed and purified.
Description
Technical Field
The invention relates to the technical field of synthesis of electroluminescent materials. Specifically, the invention relates to a preparation method of a fluorenocarbazole organic electroluminescent material intermediate with high selectivity and high yield.
Background
The OLED has an active light emitting characteristic compared with the conventional LCD, and thus, the OLED has a research focus, and the conventional fluorescent and phosphorescent OLED materials have the problems of low light emitting efficiency and short service life. Carbazole derivatives have been reported to have good hole transport properties, but when used as host materials for phosphorescent emitters, the materials still need to be improved in terms of lifetime glass transition temperature. The fluorene derivatives have good electroluminescent property, and especially can emit blue light which cannot be emitted by other materials. The fluorenocarbazole organic matter can improve the glass transition temperature of the material, has good film forming property and high stability, and the application of the fluorenocarbazole organic matter in the field of OLED can improve the performances of the product such as luminous efficiency, current efficiency, external quantum efficiency, stability, service life and the like, and improve the product performance. Therefore, the application prospect of the fluorenocarbazole organic matter in the luminescent layer material of the electroluminescent device is very considerable.
The chinese invention patent CN102482279A discloses a preparation scheme for preparing a fluorenocarbazole organic electroluminescent material, and the synthetic route thereof is as follows:
the obvious disadvantages of this preparation scheme are poor route selectivity, the need for column chromatography, high cost, difficult separation, and low yield.
Therefore, the development of a preparation method of the fluorenocarbazole organic electroluminescent material intermediate with high selectivity and high yield is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorenocarbazole organic electroluminescent material intermediate, which is characterized in that 2-amino-9, 9-dimethylfluorene is used as a raw material, and the fluorenocarbazole organic electroluminescent material intermediate with a single active site is obtained through acylation, nitration and Suzuki reaction, wherein the selectivity reaches 71%, and the reaction has outstanding advantages in the aspects of functional group selectivity and post-treatment compared with the original process.
In order to achieve the above object, the present invention provides the following technical solutions.
In a first aspect, the present invention provides a preparation method of a fluorenocarbazole-based organic electroluminescent material intermediate, which may include the steps of:
(1) performing acetylation protection on an amino-containing starting compound to obtain a first intermediate;
(2) nitrifying the acetylation-protected first intermediate obtained in the step (1) to obtain a second intermediate;
(3) performing deamination protection on the second intermediate obtained in the step (2) to obtain a third intermediate;
(4) converting the amino group of the third intermediate to a halogen substituent to give a fourth intermediate;
(5) performing Suzuki coupling reaction on the third intermediate obtained in the step (4) to obtain a fifth intermediate with fixed cyclic functional groups; and
(6) cyclizing the fifth intermediate to obtain a fluorenocarbazole organic electroluminescent material intermediate,
wherein the chemical structural formula of the starting compound is as follows:
wherein R1, R2, R3, R4, R7, and R8 are each independently selected from H, a substituted or unsubstituted C1-C12 aliphatic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group of C6-C30, or a substituted or unsubstituted fused heterocyclic group of C6-C30; r5, R6, R9, and R10 are each independently selected from the group consisting of H, -NH2A substituted or unsubstituted C1-C12 aliphatic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group of C6-C30, or a substituted or unsubstituted fused heterocyclic group of C6-C30, and at least one of R5, R6, R9, and R10 is-NH2R5 and R6 are not simultaneously-NH2R9 and R10 are not simultaneously-NH2。
In one embodiment of the first aspect, the starting compound comprises 2-amino-9, 9-dimethylfluorene.
In another embodiment of the first aspect, the fluorenocarbazole-based organic electroluminescent material intermediate includes the following compounds:
in another embodiment of the first aspect, step (1) comprises reacting the starting compound with an anhydride.
In another embodiment of the first aspect, a recrystallization purification step is further included after said step (2) and between said steps (3).
In another embodiment of the first aspect, step (5) comprises reacting the fourth intermediate with phenylboronic acid under basic conditions and in the presence of a catalyst.
In another embodiment of the first aspect, the catalyst comprises tetrakistriphenylphosphine palladium.
In another embodiment of the first aspect, said step (6) comprises reacting the fifth intermediate with triphenylphosphine in o-dichlorobenzene.
In another embodiment of the first aspect, after the step (6), a post-treatment step is further included, wherein the post-treatment step includes performing rotary evaporation and flash column chromatography on the fluorenocarbazole-based organic electroluminescent material intermediate.
In another embodiment of the first aspect, in flash column chromatography, the eluent used is a mixture of petroleum ether and ethyl acetate.
Compared with the prior art, the invention has the beneficial effects that: the reaction selectivity and the yield are high; the reaction raw materials are cheap, and the preparation process is simple; and the reaction product is easy to be post-processed and purified.
Drawings
Figure 1 shows a synthetic route according to example 1 herein.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
The fluorenocarbazole organic matter can improve the glass transition temperature of the material, has good film forming property and high stability, and the application of the fluorenocarbazole organic matter in the field of OLED can improve the performances of the product such as luminous efficiency, current efficiency, external quantum efficiency, stability, service life and the like, and improve the product performance. Therefore, the application prospect of the fluorenocarbazole organic matter in the luminescent layer material of the electroluminescent device is very considerable. However, the existing synthesis method of the fluorenocarbazole organic intermediate has the problems of poor selectivity, low yield and the like.
The invention aims to provide a preparation method of a fluorenocarbazole organic electroluminescent material intermediate, which comprises the following steps:
(1) performing acetylation protection on an amino-containing starting compound to obtain a first intermediate;
(2) nitrifying the acetylation-protected first intermediate obtained in the step (1) to obtain a second intermediate;
(3) performing deamination protection on the second intermediate obtained in the step (2) to obtain a third intermediate;
(4) converting the amino group of the third intermediate to a halogen substituent to give a fourth intermediate;
(5) performing Suzuki coupling reaction on the third intermediate obtained in the step (4) to obtain a fifth intermediate with fixed cyclic functional groups; and
(6) cyclizing the fifth intermediate to obtain a fluorenocarbazole organic electroluminescent material intermediate,
wherein the chemical structural formula of the starting compound is as follows:
wherein R1, R2, R3, R4, R7, and R8 are each independently selected from H, a substituted or unsubstituted C1-C12 aliphatic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group of C6-C30, or a substituted or unsubstituted fused heterocyclic group of C6-C30; r5, R6, R9, and R10 are each independently selected from the group consisting of H, -NH2A substituted or unsubstituted C1-C12 aliphatic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group of C6-C30, or a substituted or unsubstituted fused heterocyclic group of C6-C30, and at least one of R5, R6, R9, and R10 is-NH2R5 and R6 are not simultaneously-NH2R9 and R10 are not simultaneously-NH2。
Example 1
This example relates to the synthesis of 2-amino-9, 9-dimethylfluorene
The synthetic route of this example is shown in FIG. 1, and the numbers below each compound in FIG. 1 indicate the yield. Referring to fig. 1, the synthetic route of this example includes the following steps.
1. 2-amino-9, 9-dimethylfluorene (SM, 313.9g, 1500mmol) was added to a 3L four-necked flask, then acetic acid (1150mL, 1207.5g) was added to dissolve, and stirred well with a mechanical stirrer. Acetic anhydride (285mL, 307.8g, 3015mmol) was slowly added dropwise through an isopiestic dropping funnel (3.3h) while stirring at room temperature (around 25 ℃). After the dropwise addition, the stirring is continued at room temperature (about 25 ℃), a large amount of white precipitate is separated out in the period, and the reaction time is about 24h (6h, control 1; control 2 in 24 h). The reaction solution was poured into 5L of water and mechanically stirred at room temperature (about 25 ℃ C.) for 30 min. And (4) carrying out suction filtration under reduced pressure, and leaching a filter cake to be neutral by using water. After drying in a forced air oven (about 50 ℃) (12h), white powdery solid I (375.7g, 99.7% yield, 99.6% HPLC content) was obtained.
2. I (251.32g, 1000mmol) was added to a 3L four-necked flask, followed by the addition of propionic acid (1500mL, 1490g) to dissolve and stir well with a mechanical stirrer. The solution was cooled to about-15. + -. 2 ℃ C (internal temperature), 95% concentrated nitric acid (80mL, 120g, ca. 1816mmol) was slowly dropped (duration: 2.25h) into the reaction mixture through a constant pressure dropping funnel, and the reaction was continued at about-15. + -. 2 ℃ C (internal temperature) for 1h after completion of the dropping. Pouring the reaction solution into 9L of water, separating out a large amount of yellow solid, carrying out vacuum filtration, leaching a filter cake to be neutral by using water, drying the filter cake in a forced air oven (50 ℃) for 12 hours to obtain a crude product (293.1g), and recrystallizing in two batches.
The recrystallization operation was as follows: 150.4g of the crude product are taken and placed in a 5L four-necked flask, and after 3L of methanol and 0.75L of ethyl acetate are added, the mixture is heated under reflux until the solution is clear. Refluxing for 30min, stirring, naturally cooling to room temperature (25 deg.C + -2), crystallizing, vacuum filtering to obtain yellow needle-like solid, and washing with a small amount of methanol to obtain 89.4 g. The mother liquor is concentrated into solid for standby. Another 142.7g of crude product was placed in a 5L four-necked flask, and 2.8L of methanol and 0.70L of ethyl acetate were added thereto and then heated under reflux until the solution was clear. And continuously refluxing for 30min, stirring, naturally cooling to room temperature (25 +/-2) for crystallization, performing suction filtration to obtain a yellow needle-shaped solid, leaching the yellow needle-shaped solid with a small amount of methanol to obtain 82.5g, and concentrating the mother liquor to obtain a solid for later use. About 121.2g of the two recrystallized mother liquor concentrates were combined, and 2.4L of methanol and 0.60L of ethyl acetate were added and heated under reflux until the solution was clear. And continuously refluxing for 30min, stirring, naturally cooling to room temperature (25 +/-2) for crystallization, performing suction filtration to obtain yellow needle-shaped solid, and leaching with a small amount of methanol to obtain 38.1 g. The total amount of the obtained pure product II was 210.0g, and the yield thereof was 70.9%.
3. II (172.8g, 583.15mmol) was added to a 2L reaction flask, then dissolved in ethanol (580mL), stirred well (not completely dissolved) with a magnetic stirrer at room temperature, and 6N hydrochloric acid (580mL, 3480mmol) was added to the above solution at room temperature. The resulting solution was heated to reflux (oil bath 115 ℃ C.) and reacted for 3h (the color of the reaction gradually changed from yellow to bright orange), with disappearance of the starting material. Pouring the reaction solution into 6L of water, precipitating a large amount of bright orange solid, carrying out suction filtration under reduced pressure, leaching the filter cake to be neutral by using water, and drying the filter cake in a forced air oven (50 ℃, 12h) to obtain a pure product III (147.1g, yield 99.2%).
4. Adding III (6.10g, 23.99mmol) into a 500mL four-mouth bottle, adding DMSO (60mL) to dissolve, stirring uniformly at room temperature (25 +/-2 ℃) by mechanical stirring, slowly adding concentrated hydrochloric acid (20mL, 240mmol) under the cooling of a water bath, stirring uniformly by mechanical stirring, and cooling to an internal temperature of-5-0 ℃ by using dry ice-ethanol instead. Dropwise adding a sodium nitrite aqueous solution (1.98g, 28.70mmol dissolved in 10mL of water) at 5-0 ℃ through a constant-pressure dropping funnel, controlling the dropping speed to keep the internal temperature within the range of-5-0 ℃, and continuing to react at-5-0 ℃ for 2.5h after the addition. An aqueous solution of potassium iodide (7.96g, 47.95mmol dissolved in 20mL of water) was added dropwise from a dropping funnel at-5 to 0 ℃ C (internal temperature) to change the color from orange to brown with a large amount of bubbles. After the addition, the cooling bath was removed and the mixture was allowed to warm to room temperature (28 ℃ C.) and stirred overnight, after stirring for about 20 hours, a saturated aqueous sodium sulfite solution (20mL) was added, and a large amount of solid precipitated and appeared yellow in color. After mechanical stirring for 30min, the reaction solution was poured into 1L of water and mechanically stirred for 30 min. And (4) carrying out suction filtration under reduced pressure, and leaching a filter cake with water until a filtrate is clear. The resulting moist yellow solid was dried in a forced air oven (50 ℃, 12h) to give crude IV (8.4g, 95.9% yield). (the crude product was subjected to the next reaction without purification)
5. IV (8.33g, 22.81mmol), phenylboronic acid (2.84g, 23.29mmol) and potassium carbonate (6.31g, 45.66mmol) were charged into a 250mL four-necked flask, toluene (35mL, 30.3g) was added thereto, the mixture was dissolved with stirring at room temperature, water (23mL, 23.0g) was added thereto, and the mixture was stirred at room temperature. Nitrogen was purged four times at room temperature, followed by rapid addition of tetrakistriphenylphosphorodiamidite (0.04g, 0.035mmol) and then purging again four times at room temperature. The mixture was refluxed under nitrogen for 24 hours and then cooled to room temperature (25. + -. 2 ℃ C.), and a solid precipitated. Ethyl acetate (20mL) was added to dilute the mixture, the mixture was separated, and the aqueous phase was extracted with ethyl acetate (3X 20 mL). After the organic phases are combined, the organic phases are concentrated by rotary evaporation and then are pulped by methanol (100mL) at room temperature (25 +/-2 ℃), the pulping is carried out for 1h, the vacuum filtration is carried out, the filter cake is rinsed by a small amount of methanol (10mL) to obtain light yellow green solid powder, and the light yellow green solid powder is dried at room temperature (25 +/-2 ℃) to obtain V (6.1g, the total yield of four steps and five steps is 80%).
6. V (1.58g, 5.01mmol) and triphenylphosphine (3.29g, 12.54mmol) were charged into a 50mL reaction flask, and after addition of o-dichlorobenzene (10mL, 13g), the flask was heated to reflux (bath temperature 195 ℃ C.) and refluxed for 16h, then the flask was stopped and cooled to room temperature (25. + -. 2 ℃ C.). Most of the solvent was removed by rotary evaporation under high vacuum and flash column chromatography (petroleum ether: ethyl acetate: 5:1) gave an earthy yellow solid VI (1.14g, yield 80%).
The embodiments described above are intended to facilitate the understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments herein, and those skilled in the art can make improvements and modifications within the scope of the present invention based on the disclosure of the present invention without departing from the scope and spirit of the present invention.
Claims (8)
1. A preparation method of a fluorenocarbazole organic electroluminescent material intermediate comprises the following steps:
(1) carrying out acylation protection on an initial compound containing amino to obtain a first intermediate;
(2) nitrifying the acylation-protected first intermediate obtained in the step (1) to obtain a second intermediate;
(3) performing deamination protection on the second intermediate obtained in the step (2) to obtain a third intermediate;
(4) converting the amino group of the third intermediate to a halogen substituent to give a fourth intermediate;
(5) carrying out Suzuki coupling reaction on the fourth intermediate obtained in the step (4) to obtain a fifth intermediate with fixed cyclic functional groups; and
(6) cyclizing the fifth intermediate to obtain a fluorenocarbazole organic electroluminescent material intermediate,
wherein the starting compound is 2-amino-9, 9-dimethylfluorene;
wherein the first intermediate has the following structure:
；
the second intermediate structure is shown below:
；
the third intermediate structure is shown below:
；
the fourth intermediate structure is shown below:
(ii) a And
the fifth intermediate structure is shown below:
；
the fluorenocarbazole organic electroluminescent material intermediate is the following compound:
2. the method of claim 1, wherein step (1) comprises reacting the starting compound with an anhydride.
3. The method of claim 1, further comprising a recrystallization purification step after step (2) and between step (3).
4. The method of claim 1, wherein step (5) comprises reacting the fourth intermediate with phenylboronic acid under basic conditions and in the presence of a catalyst.
5. The method of claim 4, wherein the catalyst comprises tetrakistriphenylphosphine palladium.
6. The method of claim 1, wherein step (6) comprises reacting the fifth intermediate with triphenylphosphine in o-dichlorobenzene.
7. The method according to claim 1, further comprising a post-treatment step after step (6), wherein the post-treatment step comprises performing rotary evaporation and flash column chromatography on the fluorenocarbazole-based organic electroluminescent material intermediate.
8. A process as claimed in claim 7, wherein, in flash column chromatography, the eluent used is a mixture of petroleum ether and ethyl acetate.
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| CN102448946A (en) * | 2009-05-29 | 2012-05-09 | 默克专利有限公司 | Materials for organic electroluminescent devices |
| CN103140564A (en) * | 2010-07-30 | 2013-06-05 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent device employing organic light emitting compound as light emitting material |
| WO2017043835A1 (en) * | 2015-09-08 | 2017-03-16 | 덕산네오룩스 주식회사 | Organic electronic diode compound, organic electronic diode using same, and device therefor |
| CN106967021A (en) * | 2017-03-29 | 2017-07-21 | 江苏三月光电科技有限公司 | A kind of organic compound and its application using equal benzene as core |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102448946A (en) * | 2009-05-29 | 2012-05-09 | 默克专利有限公司 | Materials for organic electroluminescent devices |
| CN103140564A (en) * | 2010-07-30 | 2013-06-05 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent device employing organic light emitting compound as light emitting material |
| WO2017043835A1 (en) * | 2015-09-08 | 2017-03-16 | 덕산네오룩스 주식회사 | Organic electronic diode compound, organic electronic diode using same, and device therefor |
| CN106967021A (en) * | 2017-03-29 | 2017-07-21 | 江苏三月光电科技有限公司 | A kind of organic compound and its application using equal benzene as core |
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