CN112159416B - Preparation method of 4, 6-dibromo-thienofuran-1, 3-dione - Google Patents
Preparation method of 4, 6-dibromo-thienofuran-1, 3-dione Download PDFInfo
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- CN112159416B CN112159416B CN202011116799.2A CN202011116799A CN112159416B CN 112159416 B CN112159416 B CN 112159416B CN 202011116799 A CN202011116799 A CN 202011116799A CN 112159416 B CN112159416 B CN 112159416B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
Abstract
The invention discloses a preparation method of 4, 6-dibromo-thienofuran-1, 3-diketone, which takes 3, 4-dicarboxylic acid thiophene as a raw material and Br-containing‑The compound (2), DMSO and acid anhydride are used as reaction reagentsThe final product 4, 6-dibromo-thienofuran-1, 3-dione is generated through dehydration and electrophilic substitution reaction; compared with the literature method, the method has the following advantages: (1) the reaction steps are short, and the post-treatment is simple; (2) the use of toxic, volatile and difficult-to-operate bromine is avoided.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of 4, 6-dibromo-thienofuran-1, 3-diketone.
Background
4, 6-dibromo-thienofuran-1, 3-diketone serving as a monomer can participate in the synthesis of a plurality of organic polymer materials. These materials generally have good photovoltaic properties and thus can be applied to organic solar cells (Macromolecules,53(15), 6619-.
Almost all the literature at present adopts a two-step method to synthesize 4, 6-dibromo-thienofuran-1, 3-diketone, and specifically comprises the following steps: (1) synthesizing 1, 5-dibromo-3, 4-dicarboxylthiophene by taking 3, 4-dicarboxylthiophene as a raw material and bromine as a brominating agent under a heating condition; (2) acetic anhydride is used as a dehydrating agent to convert 1, 5-dibromo-3, 4-dicarboxylthiophene into 4, 6-dibromo-thienofuran-1, 3-dione. However, this method requires the use of a readily volatile, highly toxic, highly corrosive, difficult to handle bromine as the brominating agent, and the reaction needs to be carried out in stages, which further increases the cost of post-reaction treatment and product purification.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing 4, 6-dibromo-thienofuran-1, 3-dione, which has short synthesis steps and safe and easily-handled brominating reagent.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing 4, 6-dibromo-thienofuran-1, 3-dione, comprising the steps of: reacting 3, 4-dicarboxylthiophene with Br-The compound of (2), dimethyl sulfoxide (DMSO for short) and acid anhydrideAnd (3) synthesizing and reacting to obtain the product.
According to some preferred aspects of the invention, the Br-containing compound-The compound of (b) is a bromine salt and/or hydrogen bromide.
According to some specific aspects of the invention, the bromide salt is a combination of one or more selected from the group consisting of potassium bromide, sodium bromide and ammonium bromide.
According to some preferred aspects of the invention, the reaction is carried out at 100-150 ℃.
In some embodiments of the invention, the reaction is carried out at 100-120 ℃.
According to some preferred and specific aspects of the present invention, the reaction time of the reaction is 10 to 20 h.
According to some particular aspects of the invention, the anhydride is acetic anhydride and/or methanesulfonic anhydride.
According to some preferred aspects of the invention, the 3, 4-dicarboxylthiophene, the Br-containing-The feeding molar ratio of the compound (1) to the dimethyl sulfoxide to the acid anhydride is 1: 3-5: 20-40. According to a particular aspect of the invention, the 3, 4-dicarboxylthiophene, the Br-containing-The feeding molar ratio of the compound (2) to the dimethyl sulfoxide to the acid anhydride is 1:4:4: 30.
According to some particular aspects of the invention, the preparation method comprises the following specific embodiments: 3, 4-dicarboxylthiophene and Br-containing-The compound (2) and dimethyl sulfoxide are respectively added into acid anhydride, stirred at room temperature and then heated for reaction.
According to some particular aspects of the invention, the preparation method further comprises a post-treatment step comprising the steps of: and after the reaction is finished, cooling to room temperature, collecting precipitated crystals through filtration, and washing with n-hexane to obtain a final product.
According to some specific aspects of the invention, the synthetic route adopted by the preparation method is as follows:
R2o is anhydride and MBr is bromine salt.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
in the technical scheme of the invention, anhydride reacts with 3, 4-dicarboxylic thiophene to generate corresponding thienofuran-1, 3-dione and acetic acid, and Br can be in situ prepared by DMSO under an acidic condition-Oxidation to Br2Then using the in-situ formed Br2Realizing bromination of thiophene ring to generate a final product 4, 6-dibromo-thienofuran-1, 3-diketone; wherein acid is generated by dehydration and bromination of the anhydride, thereby further promoting the oxidation of Br by DMSO-Formation of Br2Compared with the literature method, the method has the following advantages: (1) the reaction steps are short, and the post-treatment is simple; (2) avoids the use of toxic, volatile and difficult-to-operate bromine, and is beneficial to industrial application.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
Example 14 preparation of 6, 6-dibromo-thienofuran-1, 3-dione
10mmol of 3, 4-dicarboxylthiophene (1.72g), 40mmol of KBr (4.76g) and 40mmol of DMSO (3.12g) were added to 300mmol of acetic anhydride (28.3mL), and the mixture was stirred at room temperature for 10 min. The temperature is increased to 100 ℃ to continue the reaction for 16h, and the temperature is reduced to room temperature. The precipitated crystal was collected by filtration and washed 2 times (10 mL. times.2) with n-hexane to obtain 2.21g of 4, 6-dibromo-thienofuran-1, 3-dione as a final product in 71% yield and 92% purity.
EXAMPLE 24 preparation of 6, 6-dibromo-thienofuran-1, 3-dione
10mmol of 3, 4-dicarboxylthiophene (1.72g), 40mmol of NaBr (4.12g) and 40mmol of DMSO (3.12g) were added to 300mmol of acetic anhydride (28.3mL), and the mixture was stirred at room temperature for 10 min. The temperature is increased to 100 ℃ to continue the reaction for 16h, and the temperature is reduced to room temperature. The precipitated crystal was collected by filtration and washed 2 times (10 mL. times.2) with n-hexane to obtain 2.34g of 4, 6-dibromo-thienofuran-1, 3-dione as a final product in 75% yield and 88% purity.
Example 34 preparation of 6, 6-dibromo-thienofuran-1, 3-dione
10mmol of 3, 4-dicarboxylthiophene (1.72g), 40mmol of NaBr (4.12g) and 40mmol of DMSO (3.12g) were added to 300mmol of acetic anhydride (28.3mL), and the mixture was stirred at room temperature for 10 min. The temperature is increased to 120 ℃ to continue the reaction for 16h, and the temperature is reduced to room temperature. The precipitated crystal was collected by filtration and washed 2 times (10 mL. times.2) with n-hexane to obtain 2.43g of 4, 6-dibromo-thienofuran-1, 3-dione as a final product in 78% yield and 93% purity.
Comparative example 1
10mmol of 3, 4-dicarboxylthiophene (1.72g) and 40mmol of NaBr (4.12g) were added to 300mmol of acetic anhydride (28.3mL), and the mixture was stirred at room temperature for 10 min. The temperature is increased to 120 ℃ to continue the reaction for 16h, and the temperature is reduced to room temperature. No target product is generated by gas chromatography detection.
Comparative example 2
10mmol of 3, 4-dicarboxylthiophene (1.72g), 40mmol of NaBr (4.12g) and 40mmol of DMSO (3.12g) were added to 300mmol of acetic anhydride (28.3mL), and the mixture was stirred at room temperature for 10 min. The temperature is increased to 50 ℃ to continue the reaction for 16h, and the temperature is reduced to room temperature. Only a small amount of target products are generated and a large amount of byproducts are generated through gas chromatography detection.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (7)
1. A method for producing 4, 6-dibromo-thienofuran-1, 3-dione, characterized by comprising the steps of: reacting 3, 4-dicarboxylthiophene with Br-Is mixed with dimethyl sulfoxide and acid anhydride, and is reacted, wherein the reaction is carried out at 100-150 ℃, and the Br is contained-The compound of (1) is a bromine salt, and the acid anhydride is acetic anhydride and/or methanesulfonic anhydride.
2. The method for producing 4, 6-dibromo-thienofuran-1, 3-dione as claimed in claim 1, characterized in that the bromine salt is a combination of one or more selected from the group consisting of potassium bromide, sodium bromide and ammonium bromide.
3. The process for producing 4, 6-dibromo-thienofuran-1, 3-dione as claimed in claim 1, characterized in that the reaction is carried out at 100-120 ℃.
4. The process for producing 4, 6-dibromo-thienofuran-1, 3-dione as claimed in claim 1, characterized in that the reaction time of the reaction is 10 to 20 hours.
5. The method for producing 4, 6-dibromo-thienofuran-1, 3-dione as claimed in claim 1, wherein the 3, 4-dicarboxylthiophene and the Br-containing compound are used as the raw materials-The feeding molar ratio of the compound (1) to the dimethyl sulfoxide to the acid anhydride is 1: 3-5: 20-40.
6. The method for producing 4, 6-dibromo-thienofuran-1, 3-dione according to claim 1, characterized by comprising the following embodiments: 3, 4-dicarboxylthiophene and Br-containing-The compound (2) and dimethyl sulfoxide are respectively added into acid anhydride, stirred at room temperature and then heated for reaction.
7. The method for producing 4, 6-dibromo-thienofuran-1, 3-dione according to claim 1, characterized in that the production method further comprises a post-treatment step, and the post-treatment step comprises the steps of: and after the reaction is finished, cooling to room temperature, collecting precipitated crystals through filtration, and washing with n-hexane to obtain a final product.
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