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Preparation method of fluorine-containing phenol

A technology for fluorine-containing phenol and fluorine-containing bromobenzene is applied in the field of preparation of fluorine-containing phenol, can solve the problems of low yield of fluorine-containing phenol, harsh reaction conditions, low yield and the like, and achieves low conventional cost of raw materials and mild reaction conditions. , the effect of high yield

Active Publication Date: 2017-06-13
湖南有色郴州氟化学有限公司
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Problems solved by technology

[0012] The above method mainly has the following disadvantages: in the method (1), the ammoniation process must be carried out under high temperature and high pressure conditions, while the diazotization reaction uses a strong acid, the reaction conditions are harsh, the equipment requirements are high, and the yield of the entire process route is low; Method (2) requires anhydrous and oxygen-free conditions, and the borate reaction will be carried out at low temperature, and the yield is greatly affected by temperature, and a large amount of solvent is needed simultaneously, and it is not easy to recycle; the organic peroxide used in method (3) is Tert-butyl peroxybenzoate (TBPB), using peroxide as an oxidant, has potential safety hazards, and the reaction produces a large amount of by-product magnesium bromide benzoate without commercial value; method (4) raw materials are not commercial products, and the price Expensive, the reaction produces a large amount of waste water containing by-product boric acid, which is not suitable for industrial production
[0013] Therefore, the above-mentioned methods for preparing fluorine-containing phenols have low yields and complex processes, all of which have relatively large limitations and are difficult to meet the needs of industrialized production.

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  • Preparation method of fluorine-containing phenol

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preparation example Construction

[0033] The present invention provides a preparation method of fluorine-containing phenol, including the following steps:

[0034] a) Mix the copper catalyst, ligand, base, fluorine-containing bromobenzene and tert-butanol, and perform etherification reaction to obtain fluorine-containing phenyl tert-butyl ether;

[0035] b) Mixing the fluorine-containing phenyl tert-butyl ether obtained in step a) with concentrated sulfuric acid and water to perform a hydrolysis reaction to obtain a fluorine-containing phenol.

[0036] The present invention firstly mixes copper catalyst, ligand, base, fluorine-containing bromobenzene and tert-butanol to carry out etherification reaction to obtain fluorine-containing phenyl tert-butyl ether. In the present invention, the copper catalyst is preferably one or more of cuprous bromide, cuprous chloride and cuprous iodide, and more preferably cuprous bromide and / or cuprous iodide. The present invention has no special restrictions on the source of the copp...

Embodiment 1

[0079] (1) Set up a mechanical stirrer, a thermometer and a spherical condenser into a 2000mL three-necked flask. Under the protection of nitrogen, 7.17g cuprous bromide (0.05mol), 82.9g potassium carbonate (0.6mol), 633g tert-butanol, 10.9g1 , 10-Phen (0.055mol) and 211.0g 3,4,5-trifluorobromobenzene (1.0mol) were added to a three-necked flask, the oil bath was heated to an internal temperature of 80℃, and reacted for 5h; after the reaction, the temperature was cooled to room temperature with stirring 9.3g of cuprous bromide was recovered by suction filtration, and then 7.9g of dry solid cuprous bromide was recovered by vacuum drying; the mother liquor was concentrated under reduced pressure on a rotary evaporator to recover 566g of tert-butanol to obtain 313g of liquid-solid mixture, and then filtered to obtain 94.0 g potassium salt; then the mother liquor is subjected to vacuum distillation under a vacuum of 7 mbar, and the fraction from 66°C to 67°C is received to obtain 182...

Embodiment 2

[0085] (1) Set up a mechanical stirrer, a thermometer and a spherical condenser into a 2000mL three-necked flask. Under the protection of nitrogen, add 4.9g cuprous chloride (0.05mol), 69.1g potassium carbonate (0.5mol), 579g tert-butanol, 6.4g TMEDA (0.055mol) and 193.0g of 3,5-difluorobromobenzene (1.0mol) were added to a three-necked flask, the oil bath was heated to an internal temperature of 80°C, and reacted for 5 hours; after the reaction, the temperature was cooled to room temperature with stirring, and 9.3g was recovered by suction filtration The cuprous chloride is vacuum dried and recovered to obtain 8.2 g of dry solid cuprous chloride; the mother liquor is concentrated under reduced pressure on a rotary evaporator to recover 506 g of tert-butanol to obtain 268 g of liquid-solid mixture, which is suction filtered to obtain 86.5 g of potassium salt; The mother liquor was subjected to vacuum distillation under a vacuum of 7 mbar, and the fraction from 66°C to 67°C was r...

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Abstract

The invention provides a preparation method of fluorine-containing phenol. The preparation method comprises the following steps of: a) mixing a copper catalyst, a ligand, alkali, fluorine-containing bromobenzene and tertiary butanol for esterification reaction to obtain fluorine-containing phenyl tertiary butyl ester; and b) mixing the fluorine-containing phenyl tertiary butyl ester obtained in the step a) with concentrated sulfuric acid and water for hydrolysis reaction to obtain the fluorine-containing phenol. Compared with the prior art, the preparation method provided by the invention directly prepares a fluorine-containing phenyl tertiary butyl ester intermediate by adopting tertiary butanol in a breakthrough manner, and then prepares the fluorine-containing phenol through the hydrolysis reaction. The process route is simple and can be continuously operated, the reaction condition is mild, and the conventional cost of raw materials is low, and the method is suitable for industrial production; moreover, the total yield of the fluorine-containing phenol prepared by the preparation method provided by the invention can reach 76% above, and the product purity is 99% above.

Description

Technical field [0001] The invention relates to the technical field of fluorine chemicals, and more specifically, to a preparation method of fluorine-containing phenol. Background technique [0002] Fluorinated phenol is a very important chemical product, especially in the field of fine chemicals, including medicine and pesticides, and has very important application prospects. At the same time, fluorine-containing phenol is also an important liquid crystal material intermediate. The introduction of fluorine atoms into the liquid crystal molecules can make the liquid crystal material have the advantages of low viscosity, fast response speed, and high resistivity. Therefore, fluorine-containing phenol is used as an intermediate for liquid crystal material development. Fluorine liquid crystal products have very broad prospects. [0003] At present, there are few process routes for synthesizing fluorine-containing phenol in the prior art, mainly including: [0004] (1) The Chinese pate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C37/055C07C39/27
CPCC07C37/055C07C37/74C07C41/01C07C39/27C07C43/225
Inventor 王刚彭智敏熊振华张振华
Owner 湖南有色郴州氟化学有限公司
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