CN112409136A - Method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diphenol by efficient clean bromination - Google Patents
Method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diphenol by efficient clean bromination Download PDFInfo
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- CN112409136A CN112409136A CN202011452576.3A CN202011452576A CN112409136A CN 112409136 A CN112409136 A CN 112409136A CN 202011452576 A CN202011452576 A CN 202011452576A CN 112409136 A CN112409136 A CN 112409136A
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- binaphthyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention relates to a method for preparing 6,6 '-dibromo-1, 1' -binaphthyl-2, 2 '-diphenol by efficient clean bromination, which comprises the steps of mixing binaphthol with a solvent, adding hydrobromic acid as a bromine source, dropwise adding hydrogen peroxide, and performing neutralization reaction, filtration, washing and recrystallization to obtain the 6, 6' -dibromo-1, 1 '-binaphthyl-2, 2' -diphenol with the content of more than 98%. The advantages are that: the preparation method is simple, the raw material cost is low, the industrialization is easy, the reaction rate is high, the reaction condition is relatively mild, and the preparation temperature is closer to the room temperature.
Description
Technical Field
The invention belongs to the field of organic synthesis and fine chemical synthesis, and particularly relates to a method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by efficient clean bromination.
Background
The 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol has wide application as an intermediate commonly used in catalysts, molecular probes, optical resins, and electronic materials, such as: for the synthesis of photoluminescent materials:chemical detector of asymmetric gluconic acid:asymmetric synthesis of ligand:and the like, wherein the asymmetric synthetic ligand can obtain better results in the asymmetric Mannich reaction:
the common method for synthesizing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol is direct bromination using elemental bromine (e.g., Mikami, Koichi, et. al., Inorg. chem. acta.1994,222(1-2), 71-5; Valentie, C.; Choi, E.; Belowich, M.E.; et. al., chem. Commun.2010,46, 4911-. Therefore, other brominating agents have been developed for use in 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol.
For example, N-bromosuccinimide (e.g., Yuji Nishii; Mitsuhiro Ikeda; Yoshihiro Hayashi; et al, J.Am.Chem.Soc.2020,142,1621-1629) is used as the brominating agent. The scheme has the disadvantages of low atom utilization rate, need of using expensive silver catalyst and the like.
Hydrobromic acid, as an easy-to-store brominating agent, is often used in conjunction with an oxidizing agent in bromination reactions. The synthesis of 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol using hydrobromic acid has been reported (for example, chinese patent CN 104649854 a), but in this scheme, dimethyl sulfoxide is used as an oxidizing agent, and a reduction product is dimethyl sulfide, so that the solvent is difficult to recycle. Moreover, the reaction temperature is relatively high, and the reaction time is relatively long.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for preparing 6,6 '-dibromo-1, 1' -binaphthyl-2, 2 '-diol by efficient clean bromination, and prepares the 6, 6' -dibromo-1, 1 '-binaphthyl-2, 2' -diol by using hydrobromic acid as a brominating agent, so that the method is easy to industrialize and has lower production cost.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the method for preparing 6,6 '-dibromo-1, 1' -binaphthyl-2, 2 '-diol by efficient clean bromination comprises the steps of mixing binaphthol with a solvent, adding hydrobromic acid as a bromine source, dropwise adding hydrogen peroxide, performing neutralization reaction, filtering, washing and recrystallizing to obtain the 6, 6' -dibromo-1, 1 '-binaphthyl-2, 2' -diol with the content of more than 98%.
The solvent is halogenated alkane.
The halogenated alkane is dichloromethane, trichloromethane or 1, 2-dichloroethane.
The mass ratio of the binaphthol to the solvent is 1 (3-15).
The mass ratio of the binaphthol to the hydrobromic acid is 1 (1-4).
The mass ratio of the binaphthol to the hydrogen peroxide is 1 (0.8-1.5).
The temperature of the reaction system is 5-45 ℃ when hydrogen peroxide is dripped.
The duration of the dropwise addition of the hydrogen peroxide is 0.5-3 hours.
The neutralization reaction is to add an alkaline aqueous solution into a reaction system.
The recrystallization solvent is 1, 2-dichloroethane.
Compared with the prior art, the invention has the beneficial effects that:
the preparation reaction rate of the 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol is high, the reaction condition is relatively mild, and the preparation temperature is closer to room temperature. The preparation method of the 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol is simple, the cost of raw materials is low, and the industrialization is easy to realize. The preparation method of the 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol has low environmental pollution, the adopted brominating agent is low in toxicity, the oxidation by-product is nontoxic water, and the wastewater can be desalted and used for producing sodium bromide and can reach the standard after biochemical treatment for discharge. The product can be separated and purified by simple filtration and recrystallization. The reaction solvent can be recycled by simple treatment, thereby reducing the production cost.
Detailed Description
The present invention is described in detail below, but it should be noted that the practice of the present invention is not limited to the following embodiments.
A method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by efficient clean bromination comprises the steps of adding 1,1 ' -binaphthyl-2, 2 ' -diol and a solvent into a four-mouth bottle, and installing a thermometer, a temperature control and stirring device and a reflux condenser pipe on the four-mouth bottle; stirring is started at normal pressure, after substrates are fully dissolved, hydrobromic acid is added, the reaction temperature is controlled to be 5-45 ℃, hydrogen peroxide is continuously dripped through a constant-pressure dropping funnel for 0.5-3 hours, and the reaction is finished after 2-6 hours;
the reaction equation is:
wherein the solvent is halogenated alkane, and the halogenated alkane is dichloromethane, trichloromethane or 1, 2-dichloroethane. The mass ratio of the 1,1 '-binaphthyl-2, 2' -diol to the solvent is 1 (3-15). The mass ratio of the 1,1 '-binaphthyl-2, 2' -diol to the hydrobromic acid is 1: (1-4). The mass ratio of the binaphthol to the hydrogen peroxide is 1 (0.8-1.5).
After the liquid phase monitoring reaction is finished, reducing the temperature of reaction liquid (the reaction liquid is substances in a four-mouth bottle) to 5-15 ℃, and adding alkaline solution into the four-mouth bottle to neutralize the reaction liquid to ensure that the pH value is 6-8. Filtering, washing, recrystallizing and drying to obtain the 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol with the content of more than 98 percent, and the yield is more than 70 percent. The alkaline aqueous solution is sodium carbonate solution. The halogenated hydrocarbon solvent used for recrystallization is specifically 1, 2-dichloroethane.
Example 1:
14.28g of 1,1 '-binaphthyl-2, 2' -diol and 123.0g of 1, 2-dichloroethane are added into a four-mouth bottle, 45.53g of hydrobromic acid (mass fraction of 48%) are added after the substrate is fully dissolved, the reaction temperature is controlled at 20 ℃, 16.71g of hydrogen peroxide (mass fraction of 27.5%) is added into the four-mouth bottle, and the mixture is dripped in 0.5 hour. After the reaction is finished, the temperature of the reaction solution is reduced to 15 ℃, sodium carbonate solution (mass fraction is 20%) is used for neutralizing the reaction solution to ensure that the pH value is 6-8, and the reaction solution is stirred until no bubbles are generated. The precipitate was filtered off and rinsed to neutrality using 30mL of 1, 2-dichloroethane and 30mL of water. Vacuum drying, yield 80%. Using dichloroethane to recrystallize, filtering and washing to obtain a white solid finished product, wherein the yield is 90%, the total yield is 72%, and the purity is 98%.
Examples 2 to 6:
the same reaction steps as those in example 1 are adopted in examples 2 to 6, except that dichloromethane is used as a solvent, the amount of hydrobromic acid is different from that of hydrogen peroxide, and the difference between examples 2 to 6 is that the reaction temperature is different, and the specific operation steps are as follows:
14.28g of 1,1 '-binaphthyl-2, 2' -diol and 130.00g of dichloromethane are added into a four-mouth bottle, 35.44g of hydrobromic acid (mass fraction of 48%) is added after a substrate is fully dissolved, the reaction temperature is controlled to be the temperature shown in 1 in the table, 14.28g of hydrogen peroxide (mass fraction of 27.5%) is added into the four-mouth bottle, and the mixture is dripped out within 0.5 hour. After the reaction, the temperature of the reaction solution is reduced to 15 ℃, sodium carbonate solution (mass fraction is 20%) is used for neutralizing the reaction solution to make the pH value of the reaction solution be 6-8, and the reaction solution is stirred until no bubbles are generated. The reaction solution before neutralization was taken out and subjected to a liquid phase test, and the results are shown in table 1.
TABLE 1 relationship of reaction temperature in methylene chloride to reaction yield
By comparison, we found that 20 ℃ is a better reaction temperature. Low temperature is not favorable for reaction, and high temperature causes more intermediates for reaction, which is not favorable for purification.
Examples 6 to 8:
the same reaction steps as those in example 1 are adopted in examples 6 to 8, except that the mass of hydrobromic acid is different from that of hydrogen peroxide, and the difference between examples 6 to 8 is a reaction solvent, and the specific operation steps are as follows:
to a four-necked flask were added 14.28g of 1,1 '-binaphthyl-2, 2' -diol and a reaction solvent, and 40.50g of hydrobromic acid (mass fraction: 48%) was added. The reaction temperature is controlled to be 20 ℃, and 14.28g of hydrogen peroxide (mass fraction is 27.5%) is slowly dropped into a four-mouth bottle. The solution was dropped over 0.5 hour. After the reaction is finished, the temperature of the reaction liquid is reduced to 15 ℃, sodium carbonate solution (mass fraction is 20%) is used for neutralizing the reaction liquid to enable the pH value to be 6-8, and stirring is carried out until no bubbles are generated. The reaction solution before neutralization was taken out and subjected to a liquid phase test, and the results are shown in Table 2.
TABLE 2 influence of reaction solvent on the reaction
By comparison, we find that 1, 2-dichloroethane has better reaction performance.
Example 9:
example 9 the same reaction procedure as in example 1 was followed, except that the mass of 1,1 '-binaphthyl-2, 2' -diol, the mass of 1, 2-dichloroethane, and the mass of hydrobromic acid were different from the mass of hydrogen peroxide.
42.84g of 1,1 '-binaphthyl-2, 2' -diphenol and 369.00g of 1, 2-dichloroethane are added into a four-mouth bottle, 141.78g of hydrobromic acid (mass fraction of 48%) is added after the substrate is fully dissolved, the reaction temperature is controlled at 20 ℃, 52.02g of hydrogen peroxide (mass fraction of 27.5%) is added into the four-mouth bottle, and the mixture is dripped over 0.5 hour. After the reaction is finished, the temperature of the reaction solution is reduced to 15 ℃, sodium carbonate solution (mass fraction is 20%) is used for neutralizing the reaction solution to ensure that the pH value is 6-8, and the reaction solution is stirred until no bubbles are generated. The precipitate was filtered off and rinsed to neutrality using 90mL of 1, 2-dichloroethane and 90mL of water. Vacuum drying, yield 81%. Using dichloroethane to recrystallize, filtering and washing to obtain a white solid finished product with the yield of 89 percent, the total yield of 72 percent and the purity of 98.1 percent.
Claims (10)
1. The method for preparing 6,6 '-dibromo-1, 1' -binaphthyl-2, 2 '-diol by efficient clean bromination is characterized by mixing binaphthol with a solvent, adding hydrobromic acid as a bromine source, dropwise adding hydrogen peroxide, and performing neutralization reaction, filtering, washing and recrystallization to obtain the 6, 6' -dibromo-1, 1 '-binaphthyl-2, 2' -diol with the content of more than 98%.
2. The process for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol according to claim 1, wherein the solvent is a halogenated alkane.
3. The process for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol according to claim 2, wherein the halogenated alkane is dichloromethane, trichloromethane or 1, 2-dichloroethane.
4. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by high-efficiency clean bromination according to claim 1, wherein the mass ratio of the binaphthol to the solvent is 1 (3-15).
5. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by high-efficiency clean bromination according to claim 1, wherein the mass ratio of binaphthol to hydrobromic acid is 1 (1-4).
6. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by high-efficiency clean bromination according to claim 1, wherein the mass ratio of the binaphthol to the hydrogen peroxide is 1 (0.8-1.5).
7. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by efficient clean bromination as claimed in claim 1, wherein the temperature of the reaction system is 5-45 ℃ when hydrogen peroxide is added dropwise.
8. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol by efficient clean bromination as claimed in claim 1, wherein the duration of dropwise adding hydrogen peroxide is 0.5-3 hours.
9. The method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol according to claim 1, wherein the neutralization reaction is performed by adding an alkaline aqueous solution into the reaction system.
10. The process for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diol according to claim 1, wherein the recrystallization solvent is 1, 2-dichloroethane.
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Citations (3)
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CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
CN104649854A (en) * | 2015-02-03 | 2015-05-27 | 北京大学 | Cheap and efficient preparation method of aryl halides |
CN109721463A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method for preparing halogenated aromatic compound |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
CN104649854A (en) * | 2015-02-03 | 2015-05-27 | 北京大学 | Cheap and efficient preparation method of aryl halides |
CN109721463A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method for preparing halogenated aromatic compound |
Non-Patent Citations (1)
Title |
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SONG SONG等: "Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization", 《ORG. LETT.》 * |
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