CN115894197A - Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone - Google Patents
Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone Download PDFInfo
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- CN115894197A CN115894197A CN202211555052.6A CN202211555052A CN115894197A CN 115894197 A CN115894197 A CN 115894197A CN 202211555052 A CN202211555052 A CN 202211555052A CN 115894197 A CN115894197 A CN 115894197A
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- 238000005904 alkaline hydrolysis reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 56
- 238000005406 washing Methods 0.000 claims abstract description 33
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 27
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 27
- 239000012074 organic phase Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000460 chlorine Substances 0.000 claims description 30
- 229910052801 chlorine Inorganic materials 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- -1 chloro compound Chemical class 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000000638 solvent extraction Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- OIHZYOFSMBHUPD-UHFFFAOYSA-N 2,6-dihydroxy-2,6-dimethyl-3,5-diphenylheptan-4-one Chemical compound CC(C)(O)C(C(=O)C(c1ccccc1)C(C)(C)O)c1ccccc1 OIHZYOFSMBHUPD-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VHCWSXJDPYQBIG-UHFFFAOYSA-N 2,6-dimethyl-3,5-diphenylheptan-4-one Chemical compound CC(C)C(C(=O)C(C(C)C)C1=CC=CC=C1)C1=CC=CC=C1 VHCWSXJDPYQBIG-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone, which comprises the steps of alkaline hydrolysis, liquid separation, sodium bicarbonate solution washing and rectification; washing an organic phase obtained by alkaline hydrolysis and liquid separation with a sodium bicarbonate solution, and controlling the pH value to be less than or equal to 8, so that the influence of residual alkali in the alkaline hydrolysis reaction on the quality of a product in the rectification process can be effectively avoided, and the quality of the product obtained by rectification is improved; compared with the traditional petroleum ether extraction mode, the method has the advantages that the alkali in the reaction system can be effectively neutralized, the water content of the obtained washing organic phase is low, organic solvent extraction is not needed, and less waste liquid is generated in the washing process.
Description
Technical Field
The invention belongs to the field of preparation of photoinitiators, and relates to an alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone.
Background
Alpha-hydroxyisobutyrophenone, also known as photoinitiator 1173, is a free radical type I photoinitiator and can be used in acrylic photocuring varnish systems coated on the surfaces of paper, metal and plastics.
The preparation process of alpha-hydroxy isobutyrophenone generally takes isobutyrophenone as a raw material and obtains a product through chlorination and alkaline hydrolysis processes; CN103613492A discloses a method for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone as a photoinitiator, which comprises the following steps: feeding 2-methyl-1-phenyl-1-propyl ketone into a chlorination reaction kettle, heating to 35-40 ℃, introducing chlorine, and keeping the temperature at about 40 ℃ for 1 hour to obtain 2-chloro-2-methyl-1-phenyl-1-propyl ketone; adding metered liquid alkali into an alkaline hydrolysis reaction kettle, adding metered 2-chloro-2-methyl-1-phenyl-1-propyl ketone, and stirring for 0.5-1 hour to finish the reaction; adding petroleum ether, stirring, extracting, separating water phase, desolventizing and recovering petroleum ether to obtain crude product 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone; pumping the crude product of 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone into a distillation still, carrying out reduced pressure distillation, and collecting product fractions to obtain a refined product of 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone; the above-mentioned technological process adopts the mode of petroleum ether extraction to collect the products after the alkaline hydrolysis reaction is finished, not only the organic solvent consumption is large, and the energy consumption of the subsequent desolventizing is high, the technological cost is high.
Therefore, the development of an alkaline hydrolysis method which does not need organic solvent extraction, has good washing effect and low impurity content in the product is still of great significance.
Disclosure of Invention
The invention aims to provide an alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone, which comprises the steps of alkaline hydrolysis, liquid separation, sodium bicarbonate solution washing and rectification; washing an organic phase obtained by alkaline hydrolysis and liquid separation with a sodium bicarbonate solution, and controlling the pH value to be less than or equal to 8, so that the influence of residual alkali in the alkaline hydrolysis reaction on the quality of a product in the rectification process can be effectively avoided, and the quality of the product obtained by rectification is improved; compared with the traditional petroleum ether extraction mode, the method has the advantages that the alkali in the reaction system can be effectively neutralized, the water content of the obtained washing organic phase is low, organic solvent extraction is not needed, and less waste liquid is generated in the washing process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone, which comprises the following steps:
(1) Mixing the chloride shown in the formula a, a sodium hydroxide solution and a phase transfer catalyst to perform alkaline hydrolysis reaction;
(2) After the alkaline hydrolysis reaction in the step (1) is finished, separating liquid to obtain an organic phase;
(3) Adding a baking soda solution into the organic phase obtained in the step (2), washing until the pH value is less than or equal to 8, such as 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 or 7.9, rectifying to remove the front-cut moisture, and obtaining the alpha-hydroxyisobutyrophenone.
In the existing alkaline hydrolysis method, after the alkaline hydrolysis reaction is finished, products are generally collected by adopting a petroleum ether extraction liquid separation mode or a direct rectification mode without extraction; in the traditional method, sodium hydroxide solution still remains in the organic phase obtained by alkaline hydrolysis and liquid separation, so that direct rectification can bring great influence on the product quality and cause high impurity content of the product; the petroleum ether extraction method has the problems of large solvent consumption, high energy consumption, large solvent loss and influence on productivity; based on solving the problems, the invention provides the alkaline hydrolysis method which does not need organic solvent extraction, has good washing effect and produces products with low impurity content.
According to the invention, researches show that the sodium hydroxide and the water remained in the alkaline hydrolysis reaction can cause great influence on the product quality; the alkaline hydrolysis method adopts baking soda solution to wash the organic phase obtained by alkaline hydrolysis liquid separation, adjusts the pH value to be less than or equal to 8, neutralizes residual alkali in the organic phase by the baking soda solution, directly carries out rectification operation and removes water in rectification before rectification, and the positive rectification part can obtain alpha-hydroxy isobutyrophenone; the purity of the obtained product can reach 99-99.5%.
Compared with the sodium bicarbonate solution washing mode, the sodium bicarbonate solution washing mode has the advantages that the water consumption is high, the waste water is more, the residual liquid caustic soda in the rectification process can generate side reaction with the product, and the impurity content of the obtained product is high; and the acid washing mode has the problem that the pH fluctuation causes the decomposition of the product.
Preferably, the step (3) is carried out without adding saturated salt solution after adding the baking soda solution for washing.
Experiments prove that after the sodium bicarbonate solution is used for washing, residual alkali can be effectively removed, the water content of the obtained washing organic phase is not high, the saturated saline solution is not required for dehydration, and on the contrary, the saturated saline solution is used for dehydration, so that the process operation steps are increased, a large amount of wastewater is generated, and the wastewater treatment cost is increased.
Preferably, the step (3) is washed by adding a baking soda solution to a pH of 7 to 8, for example 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 or 7.9, etc.
Preferably, the concentration of the baking soda solution in step (3) is 7wt% to 9wt%, such as 7.2wt%, 7.5wt%, 7.8wt%, 8wt%, 8.2wt%, 8.5wt%, or the like.
The invention adopts the baking soda solution with the concentration for washing, which can effectively neutralize residual alkali in the organic phase and the water content in the washed organic phase obtained by washing is low; compared with a water washing mode, the impurity content of the obtained product is less, and the product purity is higher.
Preferably, the concentration of the sodium hydroxide solution in step (1) is 15wt% to 25wt%, such as 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, or 24wt%, etc.
Preferably, the phase transfer catalyst of step (1) is selected from tetrabutylammonium bromide.
Preferably, the molar weight ratio of the chloride represented by formula a to the sodium hydroxide in step (1) is 1.
Preferably, the mass ratio of the chloride compound represented by formula a in step (1) to the phase transfer catalyst is 1.
In the alkaline hydrolysis method, the material proportion adopts the proportion, which is convenient for the alkaline hydrolysis reaction to be fully carried out.
Preferably, the temperature of the alkaline hydrolysis reaction in step (1) is 75 to 85 ℃, such as 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃ or 84 ℃ and the like.
Preferably, the chloride shown in the formula a in the step (1) is prepared by the following method, wherein the method comprises the following steps:
(a) Introducing chlorine into the compound of the formula b to perform chlorination reaction;
(b) After the reaction in the step (a) is finished, introducing inert atmosphere gas into the reaction liquid to remove chlorine, thereby obtaining a chloride shown in a formula a;
preferably, the temperature during the introduction of the inert atmosphere gas in step (b) is controlled to 55 to 65 ℃, for example, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃ or 64 ℃.
Preferably, the reaction apparatus is evacuated during the introduction of the inert atmosphere gas in step (b).
In the preparation method of the chloride shown in the formula a, after the chlorination reaction is finished, unreacted chlorine and HCl generated by the reaction are remained in a reaction system, if the chlorination reaction is not processed, the alkaline hydrolysis reaction is directly carried out, so that the alkali consumption is increased and is unstable, and the generated sodium hypochlorite can also cause adverse effects on the alkaline hydrolysis reaction; in the traditional mode, the alkali washing is carried out to be neutral, and then the alkaline hydrolysis reaction is carried out, so that the operation is complex, and a large amount of wastewater is generated by the alkali washing; based on the method, after the chlorination reaction is finished, chlorine and HCl in the chlorinated product are removed by introducing inert atmosphere gas, the temperature is controlled within the temperature range of 55-65 ℃ in the operation process, inorganic chlorine in the system can be effectively removed, the content of the inorganic chlorine in the obtained organic phase is low, the content is stable, and the influence on the subsequent alkaline hydrolysis working section is reduced; compared with the traditional alkali washing mode, the method is simpler to operate, and the generation of high-salinity wastewater is reduced.
Preferably, the step (b) further comprises adding a reducing agent to the reaction solution after chlorine removal.
Preferably, the reducing agent is selected from sodium sulfite.
Preferably, the ratio of the molar amount of the compound of formula b to the molar amount of the reducing agent is 1.
In the preparation method, after inert atmosphere gas is introduced for chlorine removal, part of inorganic chlorine still remains in the reaction liquid, thereby influencing the subsequent treatment; according to the invention, the trace reducing agent is added after the chlorine is removed by ventilation, so that the influence on the subsequent process can be reduced.
Preferably, the inert atmosphere gas of step (b) is selected from nitrogen.
Preferably, the temperature of the chlorination reaction in step (a) is 45 ℃ to 55 ℃, such as 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃ or 54 ℃, and the like.
Preferably, the end point of chlorine removal in step (b) is to a concentration of HCl in the chloride of formula a of 0.5g/kg or less, e.g.0.1 g/kg, 0.2g/kg, 0.3g/kg or 0.4g/kg etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) The alkaline hydrolysis method adopts baking soda solution to wash the organic phase obtained by alkaline hydrolysis liquid separation, adjusts the pH value to be less than or equal to 8, neutralizes residual alkali in the organic phase by the baking soda solution, directly carries out rectification operation and removes water in rectification before rectification, and the positive rectification part can obtain alpha-hydroxy isobutyrophenone; the obtained product has low impurity content and the purity can reach 99 to 99.5 percent;
(2) The method does not need petroleum ether organic solvent extraction, and has the advantages of simple process operation, low energy consumption, less water consumption and less generated wastewater.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone, which specifically comprises the following steps:
(1) Adding 1000kg of a compound shown as a formula b into a reaction kettle, controlling the temperature to 50 ℃, introducing chlorine, and carrying out chlorination reaction;
(2) After the reaction in the step (1) is completed, controlling the temperature to 60 ℃, introducing nitrogen to drive chlorine, and controlling c (HCl) in the chlorine hydride to be less than 0.5g/kg;
(3) After the chlorine removal in the step (2) was completed, 1800kg18% NaOH solution and 0.6kg tetrabutylammonium bromide (TBAB) were added, the temperature was raised to 80 ℃ and an alkaline hydrolysis reaction was carried out for 2 hours;
(4) After the alkaline hydrolysis reaction in the step (3) is completed, separating liquid to obtain an organic phase;
(5) And (4) adding a baking soda solution with the concentration of 8wt% into the organic phase obtained in the step (4) for washing until the pH value is 7-8, rectifying to remove the front-distilled water, and rectifying to obtain the alpha-hydroxyisobutyrophenone.
The purity of the α -hydroxyisobutyrophenone product obtained in this example was 99.0% with a yield of 98.1%.
In the step (2) of this embodiment, a chlorine-removing manner by introducing nitrogen at a controlled temperature is adopted, so that inorganic chlorine in the chloride can be effectively removed, and the obtained chloride has low content of inorganic chlorine and stable content, and is beneficial to the subsequent alkaline hydrolysis reaction; compared with the traditional way of removing chlorine by alkali washing, the method is simple to operate and reduces the generation of high-salinity wastewater.
In the step (5) of this embodiment, sodium bicarbonate solution is used for washing, which can effectively neutralize the residual alkali in the organic phase, and the obtained washed organic phase has low moisture content, and the high-purity α -hydroxyisobutyrophenone product can be obtained by directly rectifying and removing the front-distilled moisture.
Example 2
This example differs from example 1 only in that the temperature in step (2) is controlled to 25 ℃ and the other parameters and conditions are exactly the same as in example 1.
In the process of introducing nitrogen to drive chlorine, the temperature is too low, and the chlorine driving time is long.
Example 3
This example differs from example 1 only in that the temperature in step (2) is controlled to 80 ℃ and the other parameters and conditions are exactly the same as in example 1.
The purity of the α -hydroxyisobutyrophenone product obtained in this example was 98.2% with a yield of 97.1%.
In the process of introducing nitrogen to drive chlorine, the temperature is too high, and the problem of over-chlorination exists.
Example 4
This example differs from example 1 only in that 1.5kg of sodium sulfite was added to the reaction solution after the chlorine removal in step (2) was completed, and other parameters and conditions were exactly the same as those in example 1.
The purity of the α -hydroxyisobutyrophenone product obtained in this example was 99.5%, and the yield was 98.7%.
After the inert atmosphere is introduced to drive chlorine, a small amount of chlorine and hydrogen chloride can be remained in the reaction liquid, and the subsequent reaction liquid can be influenced, so that the product purity and yield are influenced, and a proper amount of sodium sulfite is added after chlorine is driven, so that the product purity and yield are improved to a certain degree.
Example 5
This example differs from example 4 only in that the amount of sodium sulfite added was replaced with 1kg and the other parameters and conditions were exactly the same as in example 1.
The purity of the α -hydroxyisobutyrophenone product obtained in this example was 99.3% with a yield of 98.5%.
Example 6
This example differs from example 1 only in that nitrogen gas was not introduced in step (2), and instead 60L of a saturated sodium bicarbonate solution was added to adjust the pH = 7-8, and the organic phase was separated; and (3) performing operations in steps (3) and (4), adding a baking soda solution in step (5), washing until the pH is = 7-8, then washing with saturated saline solution, and rectifying to obtain the alpha-hydroxyisobutyrophenone.
The purity of the α -hydroxyisobutyrophenone product obtained in this example was 99.2% with a yield of 97.8%.
In the step (2) of the embodiment, inorganic chlorine in the chloride is removed by adding a saturated sodium bicarbonate solution, the operation of the process is complex, a large amount of high-salinity wastewater is generated, and the wastewater treatment cost is high;
in the step (5) of this example, the sodium bicarbonate solution is added to wash the organic phase after washing, and the water content in the organic phase is not high, so the dehydration effect of the saturated saline solution is not obvious, and the treatment cost of the wastewater is increased.
Comparative example 1
This comparative example differs from example 1 only in that the organic phase obtained in step (4) is directly rectified without washing with a baking soda solution in step (5) to give α -hydroxyisobutyrophenone, with the other parameters and conditions being exactly the same as in example 1.
The purity of the alpha-hydroxyisobutyrophenone product obtained in this comparative example was 96.2% with a yield of 97.5%.
In the comparative example, the alkaline hydrolysis reaction is not washed after the end, the organic phase contains residual alkali, and the residual alkali can cause side reaction of the product, so that the quality and the yield of the product are reduced.
Comparative example 2
This comparative example differs from example 1 only in that the baking soda solution was replaced with water in step (5), and the other parameters and conditions were exactly the same as in example 1.
The purity of the alpha-hydroxyisobutyrophenone product obtained in this comparative example was 97.6%, and the yield was 97.8%.
The comparative example, which uses water instead of the sodium bicarbonate solution for washing, although it can reduce the amount of residual alkali, it still causes a reduction in the quality and yield of the product because the product still dissolves part of the residual alkali.
Comparative example 3
This comparative example differs from example 1 only in that the baking soda solution was replaced with a dilute hydrochloric acid solution in step (5), and the other parameters and conditions were exactly the same as in example 1.
The purity of the alpha-hydroxyisobutyrophenone product obtained in this comparative example was 97.2% with a yield of 95.7%.
This comparative example, which employs dilute hydrochloric acid instead of baking soda solution for washing, although it can reduce the amount of residual alkali, may cause a problem of product decomposition due to the possible excess of acid.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. An alkaline hydrolysis process for the preparation of α -hydroxyisobutyrophenone, comprising the steps of:
(1) Mixing the chloride shown in the formula a, a sodium hydroxide solution and a phase transfer catalyst to perform alkaline hydrolysis reaction;
(2) After the alkaline hydrolysis reaction in the step (1) is finished, separating liquid to obtain an organic phase;
(3) Adding a baking soda solution into the organic phase obtained in the step (2) for washing until the pH value is less than or equal to 8, and rectifying to remove the front-distilled water to obtain the alpha-hydroxyisobutyrophenone.
2. The alkaline hydrolysis process as claimed in claim 1, wherein the concentration of the baking soda solution in the step (3) is 7 to 9wt%.
3. The alkaline hydrolysis method according to claim 1 or 2, wherein the concentration of the sodium hydroxide solution in the step (1) is 15 to 25wt%.
4. An alkaline hydrolysis process as claimed in any one of claims 1 to 3, wherein the phase transfer catalyst of step (1) is selected from tetrabutylammonium bromide.
5. The alkaline hydrolysis process according to any one of claims 1 to 4, wherein the molar ratio of the chloride represented by the formula a to the sodium hydroxide in the step (1) is 1.1 to 1.3;
preferably, the mass ratio of the chloride shown in the formula a in the step (1) to the phase transfer catalyst is 1.
6. The alkaline hydrolysis method according to any one of claims 1 to 5, wherein the temperature of the alkaline hydrolysis reaction in the step (1) is 75 to 85 ℃.
7. The alkaline hydrolysis process as claimed in any one of claims 1 to 6, wherein the chloride represented by formula a in step (1) is prepared by a process comprising the steps of:
(a) Introducing chlorine into the compound of the formula b to perform chlorination reaction;
(b) And (b) after the reaction in the step (a) is finished, introducing inert atmosphere gas into the reaction liquid to remove chlorine, thereby obtaining the chloro compound shown in the formula (a).
8. The alkaline hydrolysis method according to claim 7, further comprising adding a reducing agent to the reaction solution after removing chlorine in the step (b);
preferably, the reducing agent is selected from sodium sulfite;
preferably, the ratio of the molar amount of the compound of formula b to the molar amount of the reducing agent is 1;
preferably, the inert atmosphere gas of step (b) is selected from nitrogen;
preferably, the temperature in the process of introducing the inert atmosphere gas in the step (b) is controlled to be 55-65 ℃.
9. The alkaline hydrolysis process according to claim 7 or 8, wherein the temperature of the chlorination reaction in step (a) is 45 ℃ to 55 ℃.
10. The alkaline hydrolysis process of any one of claims 7 to 9, wherein the chlorine removal end point in step (b) is less than or equal to 0.5g/kg HCl concentration in the chloride of formula a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202211555052.6A CN115894197A (en) | 2022-12-06 | 2022-12-06 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
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