CN111517912A - Synthetic method of 4-iodobiphenyl - Google Patents
Synthetic method of 4-iodobiphenyl Download PDFInfo
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- CN111517912A CN111517912A CN202010527517.1A CN202010527517A CN111517912A CN 111517912 A CN111517912 A CN 111517912A CN 202010527517 A CN202010527517 A CN 202010527517A CN 111517912 A CN111517912 A CN 111517912A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing 4-iodobiphenyl. The method is based on Suzuki coupling reaction, 1, 4-diiodobenzene and phenylboronic acid are used as raw materials, water is used as a solvent, the reaction is carried out for 4-12h at 50-100 ℃ under the catalysis of Pd/C, and the target product is obtained by post-processing the reaction product. The method takes water as a reaction solvent, the catalyst can be recycled, the yield is high, no pollution is caused, the method meets the requirements of environmental protection, the process is simple, the operation is convenient, and the method is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a synthesis method of 4-iodobiphenyl.
Background
Biphenyl type liquid crystal materials have the characteristics of good photostability and chemical stability, the synthesis of the liquid crystal materials attracts more and more attention, and 4-iodobiphenyl is an important intermediate for preparing photosensitive materials and liquid crystal materials; at present, a biphenyl direct iodination method is mainly adopted for preparing 4-iodobiphenyl, biphenyl and iodine are used as raw materials, ammonium persulfate or potassium persulfate is used as an oxidant, acetic acid is used as a reaction solvent, and a target product is generated in the presence of concentrated sulfuric acid and concentrated nitric acid; persulfate is a strong oxidant and is easy to decompose when meeting heat and humidity, and acetic acid, concentrated sulfuric acid and concentrated nitric acid all corrode equipment and cannot be recycled to generate a large amount of acidic waste liquid; chinese patent CN104725185A adopts Cu-La silicon dioxide mesoporous composite catalyst to replace persulfate, but still can not avoid using a large amount of concentrated sulfuric acid and concentrated nitric acid. The reaction formula of the traditional biphenyl direct iodination method is as follows:
suzuki coupling reaction, also called Suzuki coupling reaction, under the catalysis of zero-valent palladium, aryl boric acid and halogenated aromatic hydrocarbon are subjected to cross coupling, and the method is an important method for synthesizing biphenyl compounds; in order to overcome the defects of the existing technology for synthesizing 4-iodobiphenyl, the invention provides a method for synthesizing 4-iodobiphenyl by using Suzuki coupling reaction.
Disclosure of Invention
The invention aims to overcome the defects of the existing 4-iodobiphenyl synthesis method technology and provide an efficient and environment-friendly 4-iodobiphenyl synthesis method.
The technical scheme adopted by the invention is as follows:
in a water phase, Pd/C is used as a catalyst, 1, 4-diiodobenzene and phenylboronic acid are used as reaction raw materials in the presence of alkali, and 4-iodobiphenyl is generated through one-step reaction.
The reaction formula is as follows:
the synthesis method of the 4-iodobiphenyl comprises the following steps:
adding 1, 4-diiodobenzene, phenylboronic acid, alkali, a catalyst and water into a reaction bottle, stirring and heating to 50-100 ℃, preserving heat for reaction for 4-12h, cooling a reaction solution to room temperature after the reaction is finished, filtering and separating, washing a filter cake with water, recycling the catalyst, extracting a filtrate with ethyl acetate, and carrying out rotary evaporation on an organic layer to recycle the ethyl acetate to obtain a solid product.
The alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, potassium acetate, cesium carbonate and triethylamine.
The catalyst is Pd/C, and the Pd loading capacity is 5%.
The mol ratio of the 1, 4-diiodobenzene, the phenylboronic acid, the alkali and the catalyst is 1: 0.95-1.05: 1-3: 0.01-0.05.
The method of the invention has the following remarkable advantages: (1) the method takes water as a solvent, has no pollution, and avoids the generation of a large amount of acidic waste liquid in the traditional method; (2) the used Pd/C catalyst can be recycled, so that the cost is reduced; (3) high product yield, mild reaction conditions, simple process and convenient operation.
Detailed Description
Example 1
Adding 32.9g (0.1 mol) of 1, 4-diiodobenzene, 12.2g (0.1 mol) of phenylboronic acid, 21.2g (0.2 mol) of sodium carbonate and 150ml of water into a 500ml reaction bottle, uniformly stirring, adding 4.2g (0.2 mol%) of 5% Pd/C catalyst, heating to 60 ℃ for reaction for 6 hours, cooling the reaction liquid to room temperature, filtering to obtain a filter cake which is the Pd/C catalyst, washing with water, and recycling for reuse; the filtrate was extracted with ethyl acetate, the organic layer was rotary evaporated to remove the solvent to give a crude product, which was recrystallized from ethanol to give 26.6g with 95% yield.
Example 2
Adding 32.9g (0.1 mol) of 1, 4-diiodobenzene, 12.81g (0.105 mol) of phenylboronic acid, 41.46g (0.3 mol) of potassium carbonate and 200ml of water into a 500ml reaction bottle, uniformly stirring, adding 2.1g (0.1 mol) of 5% Pd/C catalyst, heating to 50 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, filtering to obtain a filter cake which is the Pd/C catalyst, washing with water, and recycling for reuse; the filtrate was extracted with ethyl acetate, the organic layer was rotary evaporated to remove the solvent to give a crude product, which was recrystallized from ethanol to give 26.18g with a yield of 93.5%.
Example 3
32.9g (0.1 mol) of 1, 4-diiodobenzene, 12.2g (0.1 mol) of phenylboronic acid, 32.5g (0.1 mol) of cesium carbonate and water (150 ml) are added into a 500ml reaction bottle, after uniform stirring, 6.3g (0.3 mol%) of 5% Pd/C catalyst is added, the temperature is raised to 80 ℃ for reaction for 6h, the reaction solution is cooled to room temperature and filtered, the filter cake is the Pd/C catalyst, and the Pd/C catalyst is recovered and reused after being washed by water. The filtrate is added with ethyl acetate for extraction, the organic layer is evaporated in a rotary way to remove the solvent, a crude product is obtained, the ethanol is recrystallized to obtain 25.9g, and the yield is 92.5%.
Example 4
32.9g (0.1 mol) of 1, 4-diiodobenzene, 12.2g (0.1 mol) of phenylboronic acid, 12g (0.3 mol) of sodium hydroxide and water (150 ml) are added into a 500ml reaction bottle, after uniform stirring, 6.3g (0.3 mol%) of 5% Pd/C catalyst is added, the temperature is raised to 60 ℃ for reaction for 6 hours, the reaction solution is cooled to room temperature and filtered, the filter cake is the Pd/C catalyst, and the Pd/C catalyst is recovered and reused after being washed by water. The filtrate was extracted with ethyl acetate, the organic layer was rotary evaporated to remove the solvent to give a crude product, which was recrystallized from ethanol to give 26.5g with a yield of 94.6%.
Claims (5)
1. A synthetic method of 4-iodobiphenyl is characterized by comprising the following steps:
adding 1, 4-diiodobenzene, phenylboronic acid, alkali and a catalyst into a reaction solvent, stirring and heating to 50-100 ℃ for reaction for 4-12h, cooling a reaction liquid to room temperature after the reaction is finished, filtering and separating, washing a filter cake with water, recovering the catalyst for reuse, extracting a filtrate with ethyl acetate, and performing rotary evaporation on an organic layer to recover the ethyl acetate to obtain a target product.
2. The method for synthesizing 4-iodobiphenyl as claimed in claim 1, wherein the reaction solvent is water.
3. The method for synthesizing 4-iodobiphenyl according to claim 1, wherein the base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, potassium acetate, cesium carbonate, and triethylamine.
4. The method for synthesizing 4-iodobiphenyl as claimed in claim 1, wherein said catalyst is Pd/C.
5. The method for synthesizing 4-iodobiphenyl as claimed in claim 1, wherein the molar ratio of 1, 4-diiodobenzene, phenylboronic acid, alkali and catalyst is 1: 0.95-1.05: 1-3: 0.01-0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010527517.1A CN111517912A (en) | 2020-06-11 | 2020-06-11 | Synthetic method of 4-iodobiphenyl |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010527517.1A CN111517912A (en) | 2020-06-11 | 2020-06-11 | Synthetic method of 4-iodobiphenyl |
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| CN111517912A true CN111517912A (en) | 2020-08-11 |
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| CN202010527517.1A Pending CN111517912A (en) | 2020-06-11 | 2020-06-11 | Synthetic method of 4-iodobiphenyl |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539679A (en) * | 2013-10-17 | 2014-01-29 | 天津市筠凯化工科技有限公司 | Method for preparing 4'-chloro-2-aminobiphenyl through palladium/carbon catalysis |
| CN104725185A (en) * | 2015-02-09 | 2015-06-24 | 许昌豪丰化学科技有限公司 | Preparation method of 4-iodobiphenyl |
-
2020
- 2020-06-11 CN CN202010527517.1A patent/CN111517912A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539679A (en) * | 2013-10-17 | 2014-01-29 | 天津市筠凯化工科技有限公司 | Method for preparing 4'-chloro-2-aminobiphenyl through palladium/carbon catalysis |
| CN104725185A (en) * | 2015-02-09 | 2015-06-24 | 许昌豪丰化学科技有限公司 | Preparation method of 4-iodobiphenyl |
Non-Patent Citations (2)
| Title |
|---|
| SARA SOBHANI ET AL.: "A hydrophilic heterogeneous cobalt catalyst for fluoride-free Hiyama, Suzuki, Heck and Hirao cross-coupling reactions in water", 《GREEN CHEMISTRY》 * |
| SARA SOBHANI ET AL.: "A novel water-dispersible/magnetically recyclable Pd catalyst for C-C cross-coupling reactions in pure water", 《ORG. PROCESS RES. DEV.》 * |
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Application publication date: 20200811 |
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