CN107353181B - Preparation method of pentafluorophenol - Google Patents
Preparation method of pentafluorophenol Download PDFInfo
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- CN107353181B CN107353181B CN201710344846.0A CN201710344846A CN107353181B CN 107353181 B CN107353181 B CN 107353181B CN 201710344846 A CN201710344846 A CN 201710344846A CN 107353181 B CN107353181 B CN 107353181B
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- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
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Abstract
The invention provides a preparation method of pentafluorophenol, which comprises the following steps: according to the method, hexafluorobenzene and potassium hydroxide are used as raw materials, a proper amount of tetrabutylammonium hydrogen sulfate, N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide and 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a 80-85% tert-butyl alcohol aqueous solution by mass fraction, the mixture is heated to slight boiling, reflux reaction is carried out for 2-3 h, a proper amount of water is added, and a tert-butyl alcohol solvent is recovered by distillation. Adjusting the pH of the residual aqueous solution to be 9-10 by using refined hydrochloric acid, adsorbing by using functional D101 macroporous adsorption resin, acidifying to be pH =1-2 by using the refined hydrochloric acid, layering, distilling an upper layer water phase to be an oil-free substance, collecting a product obtained by distillation, combining with a lower layer oil phase, rectifying, collecting a fraction with the temperature of 142 ℃ and 144 ℃, and cooling to room temperature to obtain colorless transparent crystal pentafluorophenol. The invention has simple and reasonable process, less side reaction, high reaction yield and high product purity, and can meet the quality requirements of preparing high-quality liquid crystal materials and medicines.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of pentafluorophenol.
Background
The pentafluorophenol is a valuable intermediate of medicines, liquid crystals and high molecular materials, and is mainly used for preparing a full oral medicament sofosbuvir for treating hepatitis C, a pentafluoro phenyl active ester synthesized by polypeptide and an intermediate of a high-performance polyfluoro liquid crystal material.
CN1847210A proposes a method for preparing pentafluorophenol by carrying out a Grignard reaction on bromopentafluorobenzene as a raw material to prepare a Grignard reagent and then carrying out an oxidation reaction on the Grignard reagent and peroxide. CN103420801A is prepared through displacement reaction of bromopentafluorobenzene and alkyl magnesium halide to prepare Grignard reagent, and then the Grignard reagent is oxidized with peroxide to prepare pentafluorophenol. The methods all relate to the preparation and the use of the Grignard reagent, have great potential safety hazard and great difficulty in industrial production. CN102718635A proposes a method for preparing pentafluorophenol by taking pentafluorobenzene as a raw material through lithiation, esterification, hydrolysis and oxidation in one pot, wherein the lithiation reaction and the esterification reaction are required to be carried out at a very low temperature (-60 ℃ to-80 ℃), the energy consumption of industrial production is large, and the control is not easy.
CN105016983A proposes a method for preparing pentafluorophenol by using hexafluorobenzene as an initial raw material through etherification and cracking reactions and a method for preparing pentafluorophenol by using a one-step method, wherein the two-step method for preparing pentafluorophenol through etherification and cracking is relatively complex, the total yield is only 65.6%, the method for preparing pentafluorophenol by using the one-step method is relatively simple, but anhydrous tertiary butyl alcohol is used as a solvent, and the yield is only 70%. J. Org. chem. 1991,56, 7350 and 7354 proposed to prepare pentafluorophenol by hydrolysis of hexafluorobenzene with tetrabutylammonium hydrogen sulfate as phase transfer catalyst, with large catalyst usage and 71% yield.
By adopting the conventional post-treatment purification technology, the product generally has the technical problems of high content of single impurities and difficulty in meeting the requirements of preparing high-quality liquid crystal materials and medicines, and CN106187706A provides a refining process of high-purity pentafluorophenol, but the process is complex, and the separation difficulty and the production cost are high.
Disclosure of Invention
The invention aims to solve the technical problems of more side reactions, poor solvent recycling effect, low product yield and purity and particularly high single impurity content in the prior art, and provides a pentafluorophenol preparation method with simple and reasonable process, less side reactions, high reaction yield and high product purity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of pentafluorophenol, comprising the steps of:
(1) preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
According to the weight portion, 100 portions of hexafluorobenzene, 500 portions of tert-butyl alcohol aqueous solution with the mass fraction of 80-85 percent, 65-90 portions of potassium hydroxide, 2-5 portions of tetrabutylammonium hydrogen sulfate, 0.5-1 portion of N-sulfopropyl-3-methylpyridine triflate, 0.05-0.1 portion of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthio amide and 0.02-0.05 portion of 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a reaction kettle, and the mixture is heated to slight boiling under the mechanical stirring and is refluxed for 2-3 hours. After the reaction is finished, adding 450-600 parts of water, distilling, and recovering the tert-butyl alcohol solvent;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be 9-10 by using refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 1-2BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be 1-2, layering, distilling the upper aqueous phase to be an oil-free substance, collecting the product obtained by distillation and combining the product with the lower oil phase, rectifying, collecting the fraction with the temperature of 142-144 ℃, and cooling to room temperature to obtain colorless transparent crystal pentafluorophenol.
The hexafluorobenzene, the p-aminobenzotrifluoride, the D101-Cl macroporous adsorbent resin, the tert-butyl alcohol, the potassium hydroxide, the sodium hydroxide, the tetrabutylammonium hydrogen sulfate, the N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, the N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide, the 2,2,6, 6-tetramethylpiperidine-nitrogen oxide, the sodium chloride, the ethanol, the silver nitrate and the refined hydrochloric acid are all commercially available products.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages that tetrabutylammonium hydrogen sulfate and N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate with catalyst amount are utilized, a tert-butyl alcohol aqueous solution with the mass fraction of 80-85% is used as a solvent, the catalyst amount is small, the reaction conditions are mild, side reactions are few, and the solvent can be recycled and reused.
(2) The N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthio amide and 2,2,6, 6-tetramethyl piperidine-nitrogen oxide can effectively inhibit the generation of side reactions and improve the selectivity and yield of the reaction.
(3) The functionalized D101 macroporous adsorption resin modified by the benzotrifluoride has good compatibility with fluorine-containing aromatic organic matters, is beneficial to adsorbing some organic impurities which are difficult to separate, and the prepared product has low maximum single impurity content and good product quality.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the scope of the invention.
Example 1
(1) Preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
100g of hexafluorobenzene, 500g of an 80 mass percent tert-butyl alcohol aqueous solution, 90g of potassium hydroxide, 5g of tetrabutylammonium hydrogen sulfate, 1g of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate and 0.1g of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide are added into a reaction kettle, and the mixture is heated to slight boiling under mechanical stirring and refluxed for reaction for 3 hours. After the reaction is finished, 600g of water is added, and the tertiary butanol solvent is recovered by distillation;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be =9 by refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 1BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be =2, layering, distilling the upper-layer aqueous phase to be an oil-free substance, collecting the product obtained by distillation, combining the product with the lower-layer oil phase, rectifying, collecting the fraction at 142 ℃ and 144 ℃, cooling to the room temperature to obtain 88.15g of colorless transparent crystal pentafluorophenol, wherein the yield is 89.1%, the purity (GC) is 99.91%, and the maximum single impurity content is 0.06%.
Example 2
(1) Preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
100g of hexafluorobenzene, 500g of an 80 mass percent tert-butanol aqueous solution, 90g of potassium hydroxide, 5g of tetrabutylammonium hydrogen sulfate, 1g of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, 0.1g of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide and 0.05g of 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a reaction kettle, and the mixture is heated to slight boiling under mechanical stirring and refluxed for reaction for 3 hours. After the reaction is finished, 600g of water is added, and the tertiary butanol solvent is recovered by distillation;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be =9 by refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 1BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be =2, layering, distilling the upper aqueous phase to be an oil-free substance, collecting the product obtained by distillation, combining the product with the lower oil phase, rectifying, collecting the fraction at 142 ℃ and 144 ℃, cooling to the room temperature to obtain 91.51g of colorless transparent crystal pentafluorophenol, wherein the yield is 92.5%, the purity (GC) is 99.93%, and the maximum single impurity content is 0.05%.
Example 3
(1) Preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
100g of hexafluorobenzene, 300g of an 85% by mass aqueous solution of tert-butanol, 75g of potassium hydroxide, 2g of tetrabutylammonium hydrogen sulfate, 0.75g of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, 0.1g of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide and 0.02g of 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a reaction kettle, and the mixture is heated to slight boiling under mechanical stirring and refluxed for reaction for 2 hours. After the reaction is finished, adding 450g of water, distilling, and recovering the tert-butyl alcohol solvent;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be =10 by refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 1BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be =1, layering, distilling the upper-layer aqueous phase to be an oil-free substance, collecting the product obtained by distillation, combining the product with the lower-layer oil phase, rectifying, collecting the fraction at 142 ℃ and 144 ℃, cooling to the room temperature to obtain 90.42g of colorless transparent crystal pentafluorophenol, wherein the yield is 91.4%, the purity (GC) is 99.90%, and the maximum single impurity content is 0.06%.
Example 4
(1) Preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
100g of hexafluorobenzene, 500g of an 80 mass percent tert-butanol aqueous solution, 65g of potassium hydroxide, 5g of tetrabutylammonium hydrogen sulfate, 1g of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, 0.05g of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide and 0.05g of 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a reaction kettle, and the mixture is heated to slight boiling under mechanical stirring and refluxed for reaction for 3 hours. After the reaction is finished, adding 450g of water, distilling, and recovering the tert-butyl alcohol solvent;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be =9 by refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 2BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be =1, layering, distilling the upper-layer aqueous phase to be an oil-free substance, collecting the product obtained by distillation, combining the product with the lower-layer oil phase, rectifying, collecting the fraction at 142 ℃ and 144 ℃, cooling to the room temperature to obtain 88.15g of colorless transparent crystal pentafluorophenol, wherein the yield is 89.1%, the purity (GC) is 99.90%, and the maximum single impurity content is 0.06%.
Example 5
(1) Preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
100g of hexafluorobenzene, 500g of an 80 mass percent tert-butanol aqueous solution, 90g of potassium hydroxide, 5g of tetrabutylammonium hydrogen sulfate, 0.5g of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, 0.1g of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthioamide and 0.05g of 2,2,6, 6-tetramethylpiperidine-nitrogen oxide are added into a reaction kettle, and the mixture is heated to slight boiling under mechanical stirring and refluxed for reaction for 3 hours. After the reaction is finished, 600g of water is added, and the tertiary butanol solvent is recovered by distillation;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be =10 by refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functional D101 macroporous adsorption resin for adsorption at the flow rate of 1.5BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be =2, layering, distilling the upper aqueous phase to be an oil-free substance, collecting the product obtained by distillation, combining the product with the lower oil phase, rectifying, collecting the fraction at 142 ℃ and 144 ℃, cooling to the room temperature to obtain 87.95g of colorless transparent crystal pentafluorophenol, wherein the yield is 88.9%, the purity (GC) is 99.91%, and the maximum single impurity content is 0.06%.
Comparative example 1
No tetrabutylammonium hydrogen sulfate, N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, 2,2,6, 6-tetramethylpiperidine-nitroxide, N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methylthio amide, or the like was added, and the reaction conditions and the post-treatment method were the same as in example 2, whereby 39.57g of colorless transparent crystalline pentafluorophenol was obtained in a yield of 40%, a purity (GC) of 99.85%, and a maximum single impurity content of 0.09%.
Comparative example 2
The same procedure as in example 2 was repeated except for adding tetrabutylammonium hydrogensulfate and N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate, and other reaction conditions and post-treatment were changed to give 45.50g of colorless transparent crystalline pentafluorophenol, which was obtained in 46% yield, 99.88% purity (GC) and 0.09% maximum single impurity content.
Comparative example 3
No N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate was added, and the colorless transparent crystalline pentafluorophenol 74.20g, yield 75%, purity (GC) 99.89%, maximum single impurity content 0.07% was obtained in the same manner as in example 2 except for the other reaction conditions and the post-treatment method.
Comparative example 4
The same procedure as in example 2 was repeated except for adding N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazinomethanesulphonylamide and the other reaction conditions and post-treatment to give 81.02g of colorless transparent crystalline pentafluorophenol, yield 81.9%, purity (GC) 99.88%, maximum single impurity content 0.08%.
Comparative example 5
In the step (3), the pH of the aqueous solution is not adjusted to be =9 by refined hydrochloric acid, the aqueous solution is not adsorbed by the functionalized D101 macroporous adsorption resin, the refined hydrochloric acid is directly added, the pH is adjusted to be =2, and other reaction conditions and post-treatment methods are the same as those in example 2, so that 91.02g of colorless transparent crystal pentafluorophenol is obtained, the yield is 92%, the purity (GC) is 99.5%, and the maximum single impurity content is 0.48%.
The present invention is not limited to the above-described embodiments, which are described in the above-mentioned embodiments and the description only for illustrating the principle of the present invention, and the present invention may have various insubstantial variations and modifications without departing from the spirit and scope of the present invention, which are within the scope of the claims of the present invention.
Claims (4)
1. A preparation method of pentafluorophenol is characterized by comprising the following steps:
(1) preparation of functionalized D101 macroporous adsorption resin
Sequentially adding 1000g of D101-Cl macroporous adsorption resin with chloromethylation degree of 1.5mmol/g, which is prepared by taking methyl chloride as a chloromethylation reagent, 13.5L of dimethylformamide, standing and swelling for 15h, adding 3500g of sodium chloride, 350g of p-aminobenzotrifluoride and 500g of sodium hydroxide, stirring and reacting for 48h at 65 ℃, repeatedly washing with ethanol and distilled water until no precipitate is generated after adding a silver nitrate solution, and drying to prepare the functionalized D101 macroporous adsorption resin with the functionalization degree of 1.05 mmol/g;
(2) preparation of pentafluorophenol
Adding 100 parts of hexafluorobenzene, 500 parts of 80-85 mass percent tertiary butanol aqueous solution, 65-90 parts of potassium hydroxide, 2-5 parts of tetrabutylammonium hydrogen sulfate, 0.5-1 part of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate and 0.05-0.1 part of N-methyl-2- [ (2-methylphenoxy) acetyl ] hydrazine methionine amide into a reaction kettle in parts by weight, heating to slight boiling under mechanical stirring, carrying out reflux reaction for 2-3 h, cooling to room temperature after the reaction is finished, adding 600 parts of water containing 450 impurities, distilling, and recovering a tertiary butanol solvent;
(3) refining of pentafluorophenol
Adjusting the pH of the residual aqueous solution to be 9-10 by using refined hydrochloric acid, adding the residual aqueous solution into an adsorption column filled with 1000 parts of prepared functionalized D101 macroporous adsorption resin for adsorption at the flow rate of 1-2BV/h, adding the refined hydrochloric acid into the filtrate after adsorption again, adjusting the pH to be 1-2, layering, distilling the upper aqueous phase to be oil-free, collecting the product obtained by distillation, combining the product with the lower oil phase, rectifying, and collecting the fraction at 142-144 ℃ to obtain the colorless transparent crystalline pentafluorophenol.
2. A process for preparing pentafluorophenol according to claim 1, wherein in the step (2), 0.02 to 0.05 part of 2,2,6, 6-tetramethylpiperidine-nitroxide is further added.
3. The preparation method of pentafluorophenol according to claim 1, wherein the mass ratio of the amount of the potassium hydroxide to the hexafluorobenzene in the step (2) is 0.75-0.9: 1.
4. the process for preparing pentafluorophenol according to claim 1, wherein the mass ratio of N-sulfopropyl-3-methylpyridine trifluoromethanesulfonate to hexafluorobenzene in the step (2) is 0.0075-0.01: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016983A (en) * | 2015-07-07 | 2015-11-04 | 金凯(辽宁)化工有限公司 | Preparation method of pentafluorophenol |
| CN105384603A (en) * | 2015-12-09 | 2016-03-09 | 陕西省石油化工研究设计院 | Synthesis method of poly-fluorinated phenol compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016983A (en) * | 2015-07-07 | 2015-11-04 | 金凯(辽宁)化工有限公司 | Preparation method of pentafluorophenol |
| CN105384603A (en) * | 2015-12-09 | 2016-03-09 | 陕西省石油化工研究设计院 | Synthesis method of poly-fluorinated phenol compound |
Non-Patent Citations (1)
| Title |
|---|
| 大孔吸附树脂D101的氯甲基化及功能化改性研究;董方;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110930;第B016-130页 * |
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