CN113582966A - 2-bromodibenzo [1,4] dioxane compound, preparation method and application - Google Patents
2-bromodibenzo [1,4] dioxane compound, preparation method and application Download PDFInfo
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- CN113582966A CN113582966A CN202110860132.1A CN202110860132A CN113582966A CN 113582966 A CN113582966 A CN 113582966A CN 202110860132 A CN202110860132 A CN 202110860132A CN 113582966 A CN113582966 A CN 113582966A
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- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
- C07D319/24—[b,e]-condensed with two six-membered rings
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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Abstract
The invention discloses a 2-bromodibenzo [1,4] dioxane compound, a preparation method and application thereof, relating to the technical field of organic synthesis, wherein the preparation method comprises the following steps: the method comprises the following steps: 3, 4-difluorobromobenzene and catechol are taken as raw materials, and under the alkaline condition, 2-bromodibenzo [1,4] dioxane is prepared by ring closure. The method provided by the invention has the advantages of easily available raw materials, efficient and safe preparation process, simple operation and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 2-bromodibenzo [1,4] dioxane compound, and a preparation method and application thereof.
Background
The 2-bromodibenzo [1,4] dioxane contains bromine, has high reaction activity, can realize the expansion of a molecular structure by introducing other molecular fragments through reactions such as Suzuki, Still, Buchwald-Hartwig, Heck, Miyaura and the like, and shows excellent application in the reactions. Derivatives synthesized by using the above-mentioned reaction 2-bromodibenzo [1,4] dioxane as an intermediate are widely used for synthesis of materials having a conjugated structure, and have wide applications in the fields of field effect transistors, organic light emitting diodes, and the like.
At present, the reported synthetic methods of 2-bromodibenzo [1,4] dioxane are basically prepared in two steps. Dibenzo [1,4] dioxane is prepared by using o-halophenol as a raw material (method 1: o-chlorophenol as a raw material, Russian Chemical Bulletin,67(10),1903, 1907; 2018, method 2: o-bromophenol as a raw material, RSC Advances,4(83), 44105-44116; 2014) and catechol as raw materials (method 3: catechol and o-diiodobenzene as raw materials, Tetrahedron,70(6), 1125-1132; 2014, method 4: catechol and o-dinitrobenzene as raw materials, WO 2013110135 Al), and then preparing 2-bromodibenzo [1,4] dioxane by bromine bromination (method 4: CN109776490A, method 5: Chemosphere,16(8-9), 1661-6; 1987).
In the first step of preparation, the o-halophenol in the methods 1 and 2 is a reactant and a reaction solvent, the stirring is extremely difficult during the preparation, the reaction temperature is high, great risk exists during the amplification production, the yield of the method 1 is low (45%), the expensive material Pd used in the method 2 is high, and the production cost is high. The yield in method 3 was too low (18%) and was not suitable for scale-up preparation. In method 4, the cost of o-dinitrobenzene in the current market is relatively high, the raw material is difficult to purchase, and the reaction yield is low (method 4: 41%). In the second step of preparation, bromine is used for bromination, so that the environmental pollution is great, the operation safety is lower, and the removal of polybrominated compounds is difficult in the post-treatment purification. So that the whole route is poor in realizability.
The preparation route is as follows:
the first step preparation route:
the second step of the preparation route:
in addition, in the preparation of 2-chlorodibenzo [1,4] dioxane, which is a 2-bromodibenzo [1,4] dioxane family compound reported at present, 2-chlorodibenzo [1,4] dioxane is prepared by using catechol and 2-bromo-4-chloroiodobenzene as raw materials and catalyzing the raw materials by copper powder (patent US 20180013076).
In the method, the using amount of copper powder is large (50% equivalent), the density of the copper powder is large, and a reaction system is difficult to stir uniformly and the reaction is insufficient during the amplification preparation. And a large amount of copper-containing wastewater can be generated during the post-treatment, the environmental pollution is large, the operation is complex, and great risk exists during the amplification production. And the raw material 2-bromo-4-chloroiodobenzene has higher production cost and lower yield (70%) on the basis of higher market price, fewer suppliers and unstable supply.
In addition, when the 2-chlorodibenzo [1,4] dioxane structure is used for introducing other molecular fragments to realize the expansion of the molecular structure through reactions such as Suzuki, Still, Heck, Miyaura, Buchwald-Hartwig and the like, compared with the 2-bromodibenzo [1,4] dioxane structure, the activity (halogen activity: -I > -Br > -Cl in the reaction) is poor, and no obvious advantage is generated.
The preparation route is as follows:
disclosure of Invention
In order to solve the problems, the invention provides a 2-bromodibenzo [1,4] dioxane compound and a preparation method thereof, and the method adopts easily available raw materials, has high efficiency and safety in the synthesis process, is simple to operate and is suitable for industrial production.
The invention aims to provide a preparation method of a 2-bromodibenzo [1,4] dioxane compound, which comprises the following steps:
3, 4-difluorobromobenzene and catechol are taken as raw materials, and under the alkaline condition, 2-bromodibenzo [1,4] dioxane is prepared by ring closure.
More preferably, the method specifically comprises the following steps:
under the protection of inert gas or nitrogen, 3, 4-difluorobromobenzene and catechol are mixed, then reaction solvents of N-methyl pyrrolidone and an acid-binding agent are sequentially added, nucleophilic substitution reaction is carried out for 3-4 h at 155-160 ℃, and after-treatment, the 2-bromodibenzo [1,4] dioxane is obtained.
More preferably, the molar ratio of the 3, 4-difluorobromobenzene to the catechol is 1: 1.0-1.2.
More preferably, the ratio of the 3, 4-difluorobromobenzene to the N-methylpyrrolidone is 1 g: 5-10 ml.
More preferably, the acid scavenger is potassium carbonate.
More preferably, the molar ratio of the 3, 4-difluorobromobenzene to the potassium carbonate is 1: 1.0-2.5.
More preferably, the post-treatment is to add a certain amount of aqueous solvent into the reaction system, mix the mixture evenly, filter the mixture to obtain a filter cake, wash the filter cake to neutrality, and dry the filter cake to obtain the 2-bromodibenzo [1,4] dioxane.
The second purpose of the invention is to provide a 2-bromodibenzo [1,4] dioxane compound.
The third purpose of the invention is to provide the application of the 2-bromodibenzo [1,4] dioxane compound in an organic light-emitting diode.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a 2-bromodibenzo [1,4] dioxane compound, which comprises the step of preparing 2-bromodibenzo [1,4] dioxane by ring closure of 3, 4-difluorobromobenzene and catechol under an alkaline condition. Compared with the existing 2-bromodibenzo [1,4] dioxane synthesis method, the method has the advantages of cheap and easily-obtained raw materials, simple operation, less three-waste discharge, safety, convenience, environmental protection in preparation and the like, and is mainly convenient for industrial production.
Drawings
FIG. 1 is a GC-MS spectrum of 2-bromodibenzo [1,4] dioxane as provided in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following embodiments are further described, but the present invention is not limited to the following embodiments.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
An industrial production method of a 2-bromodibenzo [1,4] dioxane compound specifically comprises the following steps:
under nitrogen protection, N-methylpyrrolidone was added to a 250mL three-necked round bottom flask in the following order: 110mL, 3, 4-difluorobromobenzene: 38.60g (0.20mol), catechol: 22.02g (0.20mol), Potassium carbonate: 66.34g (0.48mol), heating the system to 160 +/-5 ℃, carrying out heat preservation reaction for 4h, cooling to room temperature, adding 1100ml of water, stirring for 10min, filtering, washing a filter cake to be neutral, and drying the material to constant weight to obtain 41.57g of light gray solid with the yield of 79.00 percent. GC-MS calcd for C12H7BrO2(M+) 262, 262; found,262. see FIG. 1, further illustrates that the product prepared in this example is 2-bromodibenzo [1,4]]Dioxane.
The synthetic route is as follows:
example 2
An industrial production method of a 2-bromodibenzo [1,4] dioxane compound specifically comprises the following steps:
under the protection of argon, N-methylpyrrolidone is added into a 250mL three-neck round-bottom flask in sequence: 110mL, 3, 4-difluorobromobenzene: 38.60g (0.20mol), catechol: 26.43g (0.24mol), Potassium carbonate: 66.34g (0.48mol), heating the system to 160 +/-5 ℃, carrying out heat preservation reaction for 4h, cooling to room temperature, adding 1100ml of water, stirring for 10min, filtering, washing a filter cake to be neutral, and drying the material to constant weight to obtain 43.55g of light gray solid with yield of 82.76%. GC-MS calcd for C12H7BrO2(M+),262；found,262.
Example 3
An industrial production method of a 2-bromodibenzo [1,4] dioxane compound specifically comprises the following steps:
under the protection of nitrogen, sequentially adding N-methylpyrrolidone into a 1L three-neck round-bottom flask: 551mL, 3, 4-difluorobromobenzene: 192.99g (1mol), catechol: 110.11g (1mol), Potassium carbonate: 165.85g (1.2mol), heating the system to 160 +/-5 ℃, carrying out heat preservation reaction for 7h, cooling to room temperature, adding 5510ml of water, stirring for 10min, filtering, washing a filter cake to be neutral, and drying the material to constant weight to obtain 218.28g of light gray solid with the yield of 82.97%. GC-MS calcd for C12H7BrO2(M+),262；found,262.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (9)
1. A method for preparing a 2-bromodibenzo [1,4] dioxane compound, comprising the steps of:
3, 4-difluorobromobenzene and catechol are taken as raw materials, and under the alkaline condition, 2-bromodibenzo [1,4] dioxane is prepared by ring closure.
2. The method for producing a 2-bromodibenzo [1,4] dioxane compound according to claim 1, comprising the steps of:
under the protection of inert gas or nitrogen, 3, 4-difluorobromobenzene and catechol are mixed, then reaction solvents of N-methyl pyrrolidone and an acid-binding agent are sequentially added, nucleophilic substitution reaction is carried out for 3-4 h at 155-160 ℃, and after-treatment, the 2-bromodibenzo [1,4] dioxane is obtained.
3. The method for preparing a 2-bromodibenzo [1,4] dioxane compound according to claim 2, wherein the molar ratio of 3, 4-difluorobromobenzene to catechol is 1: 1.0-1.2.
4. The method for producing a 2-bromodibenzo [1,4] dioxane compound according to claim 2, wherein the 3, 4-difluorobromobenzene and N-methylpyrrolidone are used in a ratio of 1 g: 5-10 ml.
5. The method for preparing a 2-bromodibenzo [1,4] dioxane compound according to claim 2, wherein the acid-binding agent is potassium carbonate.
6. The method for preparing a 2-bromodibenzo [1,4] dioxane compound according to claim 5, wherein the molar ratio of the 3, 4-difluorobromobenzene to the potassium carbonate is 1: 1.0-2.5.
7. The method for preparing a 2-bromodibenzo [1,4] dioxane compound according to claim 2, wherein the post-treatment comprises adding a certain amount of aqueous solvent to the reaction system, mixing uniformly, filtering to obtain a filter cake, washing the filter cake to neutrality with water, and drying to obtain the 2-bromodibenzo [1,4] dioxane.
8. The 2-bromodibenzo [1,4] dioxane compound prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the 2-bromodibenzo [1,4] dioxane compound of claim 8 in an organic light emitting diode.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110740998A (en) * | 2017-11-30 | 2020-01-31 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| CN110741002A (en) * | 2017-10-18 | 2020-01-31 | 株式会社Lg化学 | Novel heterocyclic compound and organic light emitting device comprising the same |
| WO2021080334A1 (en) * | 2019-10-23 | 2021-04-29 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same, and electronic device thereof |
| JP2021086978A (en) * | 2019-11-29 | 2021-06-03 | 学校法人関西学院 | Organic electroluminescent element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741002A (en) * | 2017-10-18 | 2020-01-31 | 株式会社Lg化学 | Novel heterocyclic compound and organic light emitting device comprising the same |
| CN110740998A (en) * | 2017-11-30 | 2020-01-31 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| WO2021080334A1 (en) * | 2019-10-23 | 2021-04-29 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same, and electronic device thereof |
| JP2021086978A (en) * | 2019-11-29 | 2021-06-03 | 学校法人関西学院 | Organic electroluminescent element |
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