CN107417488A - The preparation method of 3,5 difluoro bromobenzenes - Google Patents
The preparation method of 3,5 difluoro bromobenzenes Download PDFInfo
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- CN107417488A CN107417488A CN201710446280.2A CN201710446280A CN107417488A CN 107417488 A CN107417488 A CN 107417488A CN 201710446280 A CN201710446280 A CN 201710446280A CN 107417488 A CN107417488 A CN 107417488A
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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Abstract
The invention discloses the preparation method of 3,5 difluoro bromobenzenes, comprise the following steps：2,4 difluoroanilines, dichloroethanes are added in a kettle, stirring is lower to cool, and bromine is slowly added dropwise at 10 15 DEG C in control temperature, after completion of dropwise addition, 25 DEG C are warming up to, hydrogen peroxide is added dropwise, after completion of dropwise addition, isothermal reaction, reaction process is tracked by GC, react complete after 25 40min, static, layering, organic phase is standby, and water layer is concentrated to give sodium bromide after neutralizing；Add 10% hydrochloric acid in advance in a kettle, open stirring and add above-mentioned organic phase, be cooled to 0~5 DEG C, reinforcing body natrium nitrosum, it is whether complete with starch potassium iodide paper detection reaction after adding, after the completion of reaction, after adding catalyst, sodium hypophosphite, addition to terminate, 30 50min are incubated, are to slowly warm up to 15~20 DEG C, stirring reaction, reaction process is tracked by GC, reaction is layered after terminating, and rectifying, obtains solvent and product.The preparation method is more economic and environment-friendly, and product purity is high, high income.
Description
Technical field：
The present invention relates to organic synthesis field, the preparation method of 3,5- difluoro bromobenzenes is specifically related to.
Background technology：
Bromobenzene is widely used as evil additive in motor oil and as heavy liquid solvent, is especially needing a large amount of knots
In the case of crystalline substance, in addition, it is used in some organic syntheses as raw material.
3,5- difluoro bromobenzenes are a kind of critically important fine chemical materials, and its density is 1.692g/cm3, 44.4 DEG C of flash-point,
Medicine or liquid crystal material intermediate are may be used as, there are many kinds for its preparation method at present, but mostly complex, condition
It is more harsh, and a large amount of toxic wastewaters can be produced in preparation process, raw materials requirement amount is big, and cost is high, and product yield is relatively low.
The content of the invention：
In view of the deficiencies of the prior art, the present invention provides the preparation method of one kind 3,5- difluoro bromobenzenes, it is more economical
Environmental protection, product purity is high, high income.
To achieve the above object, the present invention uses following technical scheme：
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 200-500kg dichloroethanes, stirs lower cooling, control
85kg bromines are slowly added dropwise at 10-15 DEG C in temperature, after completion of dropwise addition, are warming up to 25 DEG C, 45-65kg hydrogen peroxide is added dropwise, knot is added dropwise
Shu Hou, isothermal reaction, reaction process is tracked by GC, reacts complete after 25-40min, static, layering, organic phase is standby, water layer
Sodium bromide is concentrated to give after neutralization；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 20-50kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
30-50min, 15~20 DEG C being to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 0.5-3 hours,
Layering, rectifying, obtains solvent and product.
Preferably, the preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 300-500kg dichloroethanes, stirs lower cooling, control
85kg bromines are slowly added dropwise at 10-15 DEG C in temperature, after completion of dropwise addition, are warming up to 25 DEG C, 50-60kg hydrogen peroxide is added dropwise, knot is added dropwise
Shu Hou, isothermal reaction, reaction process is tracked by GC, reacts complete after 30-40min, static, layering, organic phase is standby, water layer
Sodium bromide is concentrated to give after neutralization；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 30-50kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
30-40min, 15~20 DEG C being to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1-2 hours, point
Layer, rectifying, obtains solvent and product.
Preferably, the preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 300kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 58kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 30min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 30kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
30min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1 hour, layering, essence
Evaporate, obtain solvent and product.
Preferably, product purity made from the preparation method is more than 99%, and yield is more than 85.9%.
The invention has the advantages that：
The present invention, as raw material, when carrying out bromo-reaction to it, while adds appropriate dioxygen with 2,4- difluoroanilines
Water, the hydrobromic acid of generation effectively can be oxidized to bromine by it, then with aniline reaction, be effectively saved the use of raw material bromine,
Cost has been saved, and has reduced the generation of toxic wastewater, it is economic and environment-friendly；
On the other hand, the present invention is by adjusting the dosage of each raw material in course of reaction, the addition sequence of each raw material and anti-
The condition answered, obtained product purity is high, is easily isolated, high income.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 300kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 58kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 30min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 30kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
30min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1 hour, layering, essence
Evaporate, obtain solvent and product.After testing, the purity of product is 99.8%, yield 90.6%.
Embodiment 2
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 200kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 45kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 25min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 20kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
50min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 3 hours, layering, essence
Evaporate, obtain solvent and product.After testing, the purity of product is 99.5%, yield 86.9%.
Embodiment 3
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 500kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 65kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 25min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 50kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
30min, 15~20 DEG C being to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 0.5 hour, layering,
Rectifying, obtain solvent and product.The purity of product is 99.6%, yield 88.5%.
Embodiment 4
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 300kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 50kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 30min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 30kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
35min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1 hour, layering, essence
Evaporate, obtain solvent and product.The purity of product is 99.3%, yield 89.5%.
Embodiment 5
The preparation method of 3,5- difluoro bromobenzenes, comprises the following steps：
(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 400kg dichloroethanes, is stirred lower cooling, is controlled temperature
At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 55kg hydrogen peroxide is added dropwise, it is permanent after completion of dropwise addition
Temperature reaction, reaction process is tracked by GC, reacts complete after 30min, static, layering, organic phase is standby, and water layer concentrates after neutralizing
Obtain sodium bromide；
(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps
Suddenly organic phase made from (1), is cooled to 0~5 DEG C, adds 67.5kg solid sodium nitrites, after adding, examined with starch potassium iodide paper
Whether complete survey reaction, after the completion of reaction, add 40kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, insulation
40min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 2 hours, layering, essence
Evaporate, obtain solvent and product.The purity of product is 99.5%, yield 87.6%.
Claims (4)
- The preparation method of 1.3,5- difluoro bromobenzenes, it is characterised in that comprise the following steps：(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 200-500kg dichloroethanes, is stirred lower cooling, is controlled temperature At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 45-65kg hydrogen peroxide, completion of dropwise addition is added dropwise Afterwards, isothermal reaction, reaction process is tracked by GC, reacts complete after 25-40min, static, layering, organic phase is standby, in water layer Sodium bromide is concentrated to give with after；(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps (1) Obtained organic phase, 0~5 DEG C is cooled to, adds 67.5kg solid sodium nitrites, after adding, detected with starch potassium iodide paper anti- Whether completely, after the completion of reaction it should add 20-50kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, be incubated 30- 50min, 15~20 DEG C being to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 0.5-3 hours, point Layer, rectifying, obtains solvent and product.
- 2. the preparation method of 3,5- difluoro bromobenzenes as claimed in claim 1, it is characterised in that comprise the following steps：(1) 129kg 2 is added in a kettle, 4- difluoroanilines, 300-500kg dichloroethanes, is stirred lower cooling, is controlled temperature At 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 50-60kg hydrogen peroxide, completion of dropwise addition is added dropwise Afterwards, isothermal reaction, reaction process is tracked by GC, reacts complete after 30-40min, static, layering, organic phase is standby, in water layer Sodium bromide is concentrated to give with after；(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps (1) Obtained organic phase, 0~5 DEG C is cooled to, adds 67.5kg solid sodium nitrites, after adding, detected with starch potassium iodide paper anti- Whether completely, after the completion of reaction it should add 30-50kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, be incubated 30- 40min, 15~20 DEG C being to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1-2 hours, layering, Rectifying, obtain solvent and product.
- 3. the preparation method of 3,5- difluoro bromobenzenes as claimed in claim 1, it is characterised in that comprise the following steps：(1) 129kg 2,4- difluoroanilines are added in a kettle, and 300kg dichloroethanes stirs lower cooling, and control temperature exists 10-15 DEG C, 85kg bromines are slowly added dropwise, after completion of dropwise addition, is warming up to 25 DEG C, 58kg hydrogen peroxide, after completion of dropwise addition, constant temperature is added dropwise Reaction, reaction process is tracked by GC, reacts complete after 30min, static, layering, organic phase is standby, and water layer is concentrated to give after neutralizing To sodium bromide；(2) hydrochloric acid that the mass concentration for adding 500kg in advance in a kettle is 10%, open stirring and add 508kg steps (1) Obtained organic phase, 0~5 DEG C is cooled to, adds 67.5kg solid sodium nitrites, after adding, detected with starch potassium iodide paper anti- Whether completely, after the completion of reaction it should add 30kg catalyst, then add 110kg sodium hypophosphites, after addition terminates, be incubated 30min, 15~20 DEG C are to slowly warm up to, stirring reaction tracks reaction process by GC, reacts complete after 1 hour, layering, rectifying, obtains molten Agent and product.
- 4. the preparation method of 3, the 5- difluoro bromobenzenes as described in claims 1 to 3 is any, it is characterised in that the preparation method system The product purity obtained is more than 99%, and yield is more than 85.9%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232170A (en) * | 2018-11-27 | 2019-01-18 | 常州大学 | A kind of preparation method of the fluoro- 1,3- dichloro-benzenes of 2,5- bis- |
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
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| US5157169A (en) * | 1992-03-26 | 1992-10-20 | Mallinckrodt Specialty Chemicals Company | Preparation of 3-halo-halobenzenes and 1-halo-3,5-dihalobenzenes |
| EP0776877A1 (en) * | 1995-12-01 | 1997-06-04 | Hoechst Aktiengesellschaft | Process for the preparation of 1-bromo-3,5-difluorobenzene |
| CN105439810A (en) * | 2015-02-15 | 2016-03-30 | 浙江永太科技股份有限公司 | Preparation method of 3,4,5-trifluorobromobenzene |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5157169A (en) * | 1992-03-26 | 1992-10-20 | Mallinckrodt Specialty Chemicals Company | Preparation of 3-halo-halobenzenes and 1-halo-3,5-dihalobenzenes |
| EP0776877A1 (en) * | 1995-12-01 | 1997-06-04 | Hoechst Aktiengesellschaft | Process for the preparation of 1-bromo-3,5-difluorobenzene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232170A (en) * | 2018-11-27 | 2019-01-18 | 常州大学 | A kind of preparation method of the fluoro- 1,3- dichloro-benzenes of 2,5- bis- |
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
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