CN1733674A - Preparation method of double(2-hydroxyl hexafluopropyl) phenol - Google Patents
Preparation method of double(2-hydroxyl hexafluopropyl) phenol Download PDFInfo
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- CN1733674A CN1733674A CN 200510028549 CN200510028549A CN1733674A CN 1733674 A CN1733674 A CN 1733674A CN 200510028549 CN200510028549 CN 200510028549 CN 200510028549 A CN200510028549 A CN 200510028549A CN 1733674 A CN1733674 A CN 1733674A
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- propyl group
- phenol
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- hexafluoro propyl
- hydroxyl hexafluoro
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Abstract
Disclosed is a preparation method of bis(2-hydroxyl hexafluopropyl) phenol, which comprises the steps of, (1) using bis(2-hydroxyl hexafluoropropyl) benzene as raw material, reacting with dibromohydamtoin (DBDMH) in solvent and sulfuric acid to obtain bromide intermediate, (2) hydrolyzing the bromide intermediate in water solution of alkalinous metal and at the presence of catalyst, and carrying out post-treatment to obtain the pure product.
Description
Technical field
The invention belongs to the preparation method field of two (2-hydroxyl hexafluoro propyl group) phenol.
Background technology
Two (2-hydroxyl hexafluoro propyl group) phenol has radioprotective and etch resistant properties, is used for radiation prevention film and erosion resistant.The method of two (the 2-hydroxyl hexafluoro propyl group) phenol of existing preparation has report in Japanese Patent jp2004083900 and U.S. Pat 2004/0106755A1, be with two (2-hydroxyl hexafluoro propyl group) benzene be raw material under the vitriol oil after nitrosonitric acid is nitrated, in the methanol solution of palladium carbon, reduce, generate diazonium salt with sulphuric acid soln and Sodium Nitrite then, in the sulphuric acid soln of copper sulfate, obtain after the hydrolysis.This method production technique is longer, and yield is low, produces a large amount of tar during hydrolysis, brings very big difficulty to aftertreatment, and wherein nitrated, reduction and diazotization reaction can produce a large amount of spent acid, waste water, waste residue, and be seriously polluted, increased cost again.
Summary of the invention
Purpose of the present invention is exactly the problems referred to above that solve prior art, and the preparation method of simple two (the 2-hydroxyl hexafluoro propyl group) phenol of a kind of yield height and technology is provided.
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, reaction formula is as follows:
Concrete steps are:
(1), be that raw material obtains the bromination intermediate compound I with the C5H6Br2N2O2 reaction in solvent and sulfuric acid with two (2-hydroxyl hexafluoro propyl group) benzene;
(2), the bromination intermediate compound I is hydrolyzed into phenol II under the basic metal aqueous solution and catalyzer condition, aftertreatment gets final product.
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein step (1) when feeding intake two (2-hydroxyl hexafluoro propyl group) benzene be 1 with the C5H6Br2N2O2 mol ratio: (0.25～5), preferably mol ratio is 1: (0.5～1).
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein the said solvent of step (1) can be lipid acid and derivative, the chloralkane etc. of C1-C5.Wherein the lipid acid of C1-C5 and derivative thereof are meant formic acid, acetic acid, ethyl acetate etc.; Chloralkane is meant methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin etc.; Preferred solvent is acetic acid and ethylene dichloride.The mass ratio of two (2-hydroxyl hexafluoro propyl group) benzene and solvent is 1: (0.1～5.0), preferred ratio is 1: (0.5～2).
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein the temperature of step (1) bromination reaction is at 15-100 ℃.The temperature of optimizing is 30-60 ℃; The bromination reaction time is 8-20 hour.
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, the said basic metal aqueous solution of step (2) wherein, its used alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or hydrated barta etc., is preferably hydrated barta; The mol ratio of bromination intermediate and hydrated barta is 1: (0.25～5) is preferably 1: (1～4).
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein the said catalyzer of step (2) can be following a kind of or its mixture: inorganic copper, mantoquita or cupric organic compound, wherein inorganic copper is meant copper, mantoquita is meant cupric oxide or copper halide etc., the cupric organic compound is meant copper 8-quinolinolate etc., be preferably copper 8-quinolinolate, the mass ratio of bromination intermediate and catalyzer is 1: (1/1000)～1, preferred ratio is 1: (1/1000)～(1/30).
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein the mass ratio of said bromination intermediate of step (2) and water is 1: (1～10) is preferably 1: (2～5).
The preparation method of two (2-hydroxyl hexafluoro propyl group) phenol of the present invention, wherein the temperature of reaction of step (2) is 130-185 ℃, the temperature of reaction of optimization is 150-170 ℃; Reaction pressure 0.3-1.4MPa, reaction times 2-10 hour.At last with the product that obtains through neutralization, extraction, layering, precipitation, the rectifying aftertreatment obtains content＞99.0% of two (2-hydroxyl hexafluoro propyl group) phenol.
Beneficial effect of the present invention: compare with two (the 2-hydroxyl hexafluoro propyl group) phenol processes of existing preparation, the present invention has not only shortened the technology distance, has improved product yield, and aftertreatment is more simple, the three wastes in the production significantly reduce, thereby production cost is significantly reduced.
Specific embodiment
Following type reaction is used for illustrating the present invention, for those skilled in the art within the technical scheme that the simple replacement done of invention or improvement etc. are all belonged to the present invention and protected.
Embodiment 1: bromination reaction
The 1000ml band stirs four-hole glass reaction bottle, is furnished with thermometer and reflux condensing tube.In reaction flask, add 600g acetic acid, be added dropwise to the 300g vitriol oil under stirring, add two (2-hydroxyl hexafluoro propyl group) the benzene 300g of raw material down fast at 20-40 ℃; Under 40-45 ℃, add solid C5H6Br2N2O2 104.6g in batches, add 60 ℃ of reactions of back insulation reaction in 14 hours and finish.System is slowly injected 1600g water, and standing demix gets lower floor's organic phase, and with 300ml water washing organic phase twice, dry back rectifying gets bromination intermediate 210g.
Embodiment 2～10: bromination reaction
Experimental working technique is with embodiment 1, and other bromination reaction condition and parameter see Table one.
The table monobromination is reacted the reaction conditions parameter of each embodiment
| Bromination reaction | Two (2-hydroxyl hexafluoro propyl group) benzene | Type of solvent | Solvent/g | C5H6Br2N2O2/mol | Temperature of reaction/℃ | Reaction times/h | The bromination intermediate |
| Embodiment 1 | 300g/0.704mol | Acetic acid | 600 | 0.366 | 60 | 14 | 210g |
| Embodiment 2 | 300g | Ethylene dichloride | 400 | 0.420 | 60 | 12 | 230g |
| Embodiment 3 | 300g | Acetic acid | 300 | 0.630 | 40 | 11 | 300g |
| Embodiment 4 | 300g | Acetic acid | 300 | 0.731 | 30 | 8 | 250g |
| Embodiment 5 | 300g | Acetic acid | 300 | 0.176 | 35 | 10 | 140g |
| Embodiment 6 | 300g | Acetic acid | 300 | 3.52 | 40 | 16 | 70g |
| Embodiment 7 | 300g | Acetic acid | 30 | 0.63 | 40 | 10 | 80g |
| Embodiment 8 | 300g | Acetic acid | 1500 | 0.63 | 40 | 10 | 270g |
| Embodiment 9 | 300g | Acetic acid | 300 | 0.63 | 15 | 18 | 60g |
| Embodiment 10 | 300g | Acetic acid | 150 | 0.63 | 100 | 8 | 90g |
Embodiment 11: hydrolysis reaction
In 1000ml band agitated autoclave, throw bromination intermediate 100g, barium hydroxide octahydrate 15.6g, water 200g and 2g8-copper quinolinate are behind twice of the nitrogen replacement of 5kgf, after not leaking in 20 minutes with the 6kg pressure testing, be vented to normal pressure, be warmed up to 180 ℃, pressure is at 1.4Mpa, and insulation reaction reaction in 10 hours is finished.Cool to room temperature, go in the 1000ml band stirred glass still, drip the 25g30%HCl neutralization, PH=2-3, respectively with merging organic phase after 200g and the 100g ethyl acetate extracting twice, with twice washing of 100g moisture after drying, rectifying can get two (the 2-hydroxyl hexafluoro propyl group) phenol (content＞99%) of 18g product.
Embodiment 12～21: hydrolysis reaction
Experimental working technique is with embodiment 11, and other hydrolysis reaction condition and parameter see Table two.
Table two
| Hydrolysis reaction | The bromination intermediate | Catalyzer | Alkali | Water | Temperature of reaction | Reaction pressure | Product |
| Embodiment 11 | 100g/ 0.198mol | Copper 8-quinolinolate 2g | Barium hydroxide octahydrate 0.0495mol | 200g | 180℃ | 1.4Mpa | 18g |
| Embodiment 12 | 100g | Copper 8-quinolinolate 3g | Barium hydroxide octahydrate 0.317mol | 245g | 170℃ | 1.2 Mpa | 40g |
| Embodiment 13 | 100g | Copper 8-quinolinolate 0.1g | Barium hydroxide octahydrate 0.476mol | 245g | 150℃ | 1.0 Mpa | 35g |
| Embodiment 14 | 100g | Copper 8-quinolinolate 100g | Barium hydroxide octahydrate 0.476mol | 370g | 140℃ | 0.8 Mpa | 25g |
| Embodiment 15 | 100g | Copper 8-quinolinolate 3g | Barium hydroxide octahydrate 0.817mol | 500g | 135℃ | 0.6 Mpa | 22g |
| Embodiment 16 | 100g | Copper 8-quinolinolate 3g | Barium hydroxide octahydrate 0.476mol | 370g | 145℃ | 1.1 Mpa | 25g |
| Embodiment 17 | 100g | Copper 8-quinolinolate 3g | Potassium hydroxide 0.2mol | 100g | 130℃ | 0.8 Mpa | 10g |
| Embodiment 18 | 100g | Copper powder 3.33g | Barium hydroxide octahydrate 0.476mol | 1000g | 185℃ | 0.6 Mpa | 18g |
| Embodiment 19 | 100g | Cupric oxide 18g | Barium hydroxide octahydrate 0.99mol | 300g | 145℃ | 0.3 Mpa | 22g |
| Embodiment 20 | 100g | Copper 8-quinolinolate 3g | Barium hydroxide octahydrate 0.476mol | 100g | 145℃ | 0.3 Mpa | 24g |
| Embodiment 21 | 100g | Copper 8-quinolinolate 3g | Barium hydroxide octahydrate 0.476mol | 1000g | 145℃ | 0.6 Mpa | 15g |
By above embodiment as seen, with two (2-hydroxyl hexafluoro propyl group) benzene is that raw material obtains the bromination intermediate compound I with the C5H6Br2N2O2 reaction in solvent and sulfuric acid, the technical scheme that again the bromination intermediate compound I is hydrolyzed into phenol II under the basic metal aqueous solution and catalyzer condition is enforceable, can obtain two (the 2-hydroxyl hexafluoro propyl group) phenol of pure product through simple aftertreatment.
Claims (23)
1. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol, its reaction formula is as follows:
Concrete steps are:
(1), be that raw material obtains the bromination intermediate compound I with the C5H6Br2N2O2 reaction in solvent and sulfuric acid with two (2-hydroxyl hexafluoro propyl group) benzene;
(2), the bromination intermediate compound I is hydrolyzed into two (2-hydroxyl hexafluoro propyl group) phenol II under the basic metal aqueous solution and catalyzer condition, carry out aftertreatment then.
2. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that, step (1) when feeding intake the mol ratio of two (2-hydroxyl hexafluoro propyl group) benzene and C5H6Br2N2O2 be 1: 0.25～5.
3. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 2 is characterized in that the mol ratio of two (2-hydroxyl hexafluoro propyl group) benzene and C5H6Br2N2O2 is 1: 0.5～1.
4. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that the said solvent of step (1) is lipid acid and derivative or the chloralkane of C1-C5.
5. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 4 is characterized in that the said solvent of step (1) is formic acid, acetic acid, ethyl acetate, methylene dichloride, ethylene dichloride, chloroform or tetracol phenixin.
6. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 5 is characterized in that the said solvent of step (1) is acetic acid or ethylene dichloride.
7. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that, the mass ratio of the said solvent of step (1) and two (2-hydroxyl hexafluoro propyl group) benzene is 0.1～5: 1.
8. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 7 is characterized in that, the mass ratio of the said solvent of step (1) and two (2-hydroxyl hexafluoro propyl group) benzene is 0.5～2: 1.
9. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that the temperature of reaction of step (1) is 15-100 ℃.
10. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 9 is characterized in that the temperature of reaction of step (1) is 30-60 ℃.
11. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that, the said basic metal aqueous solution of step (2), and its used alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or hydrated barta.
12. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 11 is characterized in that used alkali is hydrated barta during step (2) hydrolysis.
13. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 11 is characterized in that the mol ratio of bromination intermediate compound I and hydrated barta is 1: 0.25～5 during step (2) hydrolysis.
14. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 13 is characterized in that the mol ratio of bromination intermediate compound I and hydrated barta is 1: 1～4 during step (2) hydrolysis.
15. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that the mass ratio of bromination intermediate compound I and water is 1: 1～10 during step (2) hydrolysis.
16. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 15 is characterized in that the mass ratio of bromination intermediate compound I and water is 1: 2～5 during step (2) hydrolysis.
17. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that used catalyzer can be following a kind of or its mixture during step (2) hydrolysis: inorganic copper, mantoquita or cupric organic compound.
18. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 17 is characterized in that used catalyzer is meant copper, cupric oxide, copper halide or copper 8-quinolinolate during step (2) hydrolysis.
19. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 18 is characterized in that used catalyzer is a copper 8-quinolinolate during step (2) hydrolysis.
20. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that the mass ratio of bromination intermediate compound I and catalyzer is 1 during step (2) hydrolysis: (1/1000)～1.
21. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 20 is characterized in that the mass ratio of bromination intermediate compound I and catalyzer is 1 during step (2) hydrolysis: (1/100)～(1/30).
22. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 1 is characterized in that the temperature of reaction of step (2) is 130-185 ℃.
23. the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol as claimed in claim 22 is characterized in that the temperature of reaction of step (2) is 150-170 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100285492A CN1300076C (en) | 2005-08-05 | 2005-08-05 | Preparation method of double(2-hydroxyl hexafluopropyl) phenol |
| JP2006210193A JP5036243B2 (en) | 2005-08-05 | 2006-08-01 | Method for producing 3,5-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100285492A CN1300076C (en) | 2005-08-05 | 2005-08-05 | Preparation method of double(2-hydroxyl hexafluopropyl) phenol |
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| CN1733674A true CN1733674A (en) | 2006-02-15 |
| CN1300076C CN1300076C (en) | 2007-02-14 |
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| CNB2005100285492A Active CN1300076C (en) | 2005-08-05 | 2005-08-05 | Preparation method of double(2-hydroxyl hexafluopropyl) phenol |
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| CN (1) | CN1300076C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830793A (en) * | 2010-05-13 | 2010-09-15 | 中科院广州化学有限公司 | Method for preparing hydroxyl-substituted phenylacetic acid compound |
| CN103641692A (en) * | 2013-11-27 | 2014-03-19 | 北京航空航天大学 | Preparation of novel fluorine-containing bisphenol compound |
| CN105541597A (en) * | 2015-12-29 | 2016-05-04 | 中山大学 | Preparation method of 2,4-dihydroxyphenyl acetic acid |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075493B2 (en) * | 1989-06-26 | 1995-01-25 | セントラル硝子株式会社 | Process for producing bis (2-hydroxyhexafluoro-2-propyl) benzene derivative |
| JP2857745B2 (en) * | 1996-02-22 | 1999-02-17 | 工業技術院長 | Novel fluorine-containing compound for biological imaging using <19F> -NMR |
| CA2374595A1 (en) * | 1999-06-11 | 2000-12-21 | Merck & Co., Inc. | Process for the synthesis of 3,5-bis(trifluoromethyl)-bromobenzene |
| JP4212307B2 (en) * | 2002-06-24 | 2009-01-21 | セントラル硝子株式会社 | Method for producing fluorine-containing styrene polymerizable monomer and intermediate compound used therefor |
| JP4410508B2 (en) * | 2002-08-07 | 2010-02-03 | セントラル硝子株式会社 | Fluorine-containing compounds and their polymer compounds |
| US7125943B2 (en) * | 2002-08-07 | 2006-10-24 | Central Glass Company, Limited | Fluorine-containing compounds and their polymers useful for anti-reflection film materials and resist compositions |
-
2005
- 2005-08-05 CN CNB2005100285492A patent/CN1300076C/en active Active
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2006
- 2006-08-01 JP JP2006210193A patent/JP5036243B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830793A (en) * | 2010-05-13 | 2010-09-15 | 中科院广州化学有限公司 | Method for preparing hydroxyl-substituted phenylacetic acid compound |
| CN101830793B (en) * | 2010-05-13 | 2014-01-15 | 中科院广州化学有限公司 | Method for preparing hydroxyl-substituted phenylacetic acid compound |
| CN103641692A (en) * | 2013-11-27 | 2014-03-19 | 北京航空航天大学 | Preparation of novel fluorine-containing bisphenol compound |
| CN103641692B (en) * | 2013-11-27 | 2015-07-08 | 北京航空航天大学 | Preparation of novel fluorine-containing bisphenol compound |
| CN105541597A (en) * | 2015-12-29 | 2016-05-04 | 中山大学 | Preparation method of 2,4-dihydroxyphenyl acetic acid |
| CN105541597B (en) * | 2015-12-29 | 2018-06-01 | 中山大学 | A kind of preparation method of 2,4- dihydroxyphenyl acetic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1300076C (en) | 2007-02-14 |
| JP5036243B2 (en) | 2012-09-26 |
| JP2007045820A (en) | 2007-02-22 |
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Address after: Building No. 200, Lane 2891, Qilian Mountain South Road, Putuo District, Shanghai Co-patentee after: CENTRAL GLASS Co.,Ltd. Patentee after: Shanghai Kangpeng Science and Technology Co.,Ltd. Address before: 2003 No. 3, Lane 1273, Tongpu Road, Putuo District, Shanghai Co-patentee before: CENTRAL GLASS Co.,Ltd. Patentee before: SHANGHAI CHEMSPEC Corp. Address after: No. 3, Lane 1273, Tongpu Road, Putuo District, Shanghai Co-patentee after: CENTRAL GLASS Co.,Ltd. Patentee after: SHANGHAI CHEMSPEC Corp. Address before: 2003 No. 3, Lane 1273, Tongpu Road, Putuo District, Shanghai Co-patentee before: CENTRAL GLASS Co.,Ltd. Patentee before: Shanghai Kangpeng Chemical Co.,Ltd. |