CN115650836B - Synthesis process of 2-hydroxy-4-methoxyl benzophenone - Google Patents
Synthesis process of 2-hydroxy-4-methoxyl benzophenone Download PDFInfo
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- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012043 crude product Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- WWVXYKPKRAMYDP-UHFFFAOYSA-N (2,4-dimethoxyphenyl)-phenylmethanone Chemical compound COC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 WWVXYKPKRAMYDP-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 5
- 230000011987 methylation Effects 0.000 description 5
- 238000007069 methylation reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- WBGWGHYJIFOATF-UHFFFAOYSA-M potassium;methyl sulfate Chemical compound [K+].COS([O-])(=O)=O WBGWGHYJIFOATF-UHFFFAOYSA-M 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
Abstract
The invention provides a synthesis process of 2-hydroxy-4-methoxyl benzophenone, which takes 2, 4-dihydroxyl benzophenone and dimethyl sulfate as raw materials to prepare 2-hydroxy-4-methoxyl benzophenone through two-stage catalytic reaction; wherein the catalyst in the first stage is strong alkali weak acid salt, and the reaction temperature is 60-140 ℃; the catalyst in the second stage is strong alkali, and the reaction temperature is 150-170 ℃. According to the scheme provided by the invention, the methyl in the dimethyl sulfate is fully utilized through the second-stage strong alkali, so that the consumption of the dimethyl sulfate is reduced, the production cost is reduced, the problem of high COD pollutant discharge amount of the washing wastewater is solved, and the environmental-friendly treatment difficulty is reduced.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and in particular relates to a synthesis process of 2-hydroxy-4-methoxyl benzophenone.
Background
2-Hydroxy-4-methoxyl diphenyl ketone (UV-9) can be used as a light stabilizer and also can be used as an intermediate for synthesizing an ultraviolet absorber 2-hydroxy-4-methoxyl diphenyl ketone-5-sulfonic acid, can effectively absorb ultraviolet light of 200-400 nm, hardly absorbs visible light, can be used for paint and various plastic products, is particularly suitable for light-colored transparent products, is a good cosmetic additive, and is increasingly valued in the plastic and rubber industry.
At present, the main method for producing 2-hydroxy-4-methoxybenzophenone at home and abroad is obtained by etherification reaction of 2, 4-dihydroxybenzophenone and dimethyl sulfate, the method takes dimethyl sulfate as a methylating agent, and the dimethyl sulfate and the 2, 4-dihydroxybenzophenone are subjected to etherification reaction under the action of sodium carbonate and the like to obtain the 2-hydroxy-4-methoxybenzophenone.
CN110128253 a discloses that 2, 4-dihydroxybenzophenone and dimethyl carbonate are used as raw materials, and the reaction is carried out under medium temperature and medium pressure conditions, and although green and environment-friendly dimethyl carbonate raw materials are used, the etherification selectivity is poor, so that the byproduct 2, 4-dimethoxybenzophenone in the reaction system is larger, the yield is lower, and the problems of harsh reaction conditions, long reaction time, high cost and the like exist in the process.
Therefore, the research and development cost is proper, the product yield is high, the quality is good, and the novel process for preparing the 2-hydroxy-4-methoxyl benzophenone is high in efficiency.
Disclosure of Invention
The synthesis process of the 2-hydroxy-4-methoxyl benzophenone can realize the complete utilization of methyl in dimethyl sulfate, reduce the consumption of the dimethyl sulfate, reduce the production cost, reduce the emission of pollutants and reduce the environmental protection treatment difficulty.
The technical scheme of the invention is that the synthesis process of 2-hydroxy-4-methoxybenzophenone takes 2, 4-dihydroxybenzophenone and dimethyl sulfate as raw materials, and is catalyzed by a first catalyst to perform a first-stage reaction in a solvent environment, then a system solvent is distilled out, and a second catalyst is added to perform a second-stage reaction to prepare 2-hydroxy-4-methoxybenzophenone; wherein the first catalyst is strong alkali weak acid salt, and the reaction temperature is 60-140 ℃; the second catalyst is strong alkali and the reaction temperature is 150-170 ℃.
Further, the first catalyst is one of potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the first stage reaction time is 2-6 hours.
Further, the second catalyst is one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Further, the second stage reaction time is 2-4 hours.
Further, the molar ratio of the 2, 4-dihydroxybenzophenone and the dimethyl sulfate is 1:0.5-0.7.
Further, the dosage of the first catalyst and the dosage of the 2, 4-dihydroxybenzophenone are 0.5-1: 1.
Further, the dosage of the second catalyst and the dosage of the 2, 4-dihydroxybenzophenone are 0.1 to 0.5:1.
Further, when the reaction raw material is added, the adopted solvent is one of n-hexane, cyclohexane, toluene and n-heptane, and the addition amount of the solvent is 1 to 3 times of the mass of the 2-hydroxy-4-methoxybenzophenone.
Further, after the second-stage reaction is finished, the system is cooled to below 100 ℃, water is added and mixed uniformly, then the water phase and the organic phase are separated, the organic phase is distilled under reduced pressure to obtain a crude product of 2-hydroxy-4-methoxybenzophenone, and the crude product is recrystallized and refined to obtain the 2-hydroxy-4-methoxybenzophenone product.
The invention has the following beneficial effects:
1. According to the invention, dimethyl sulfate is used as a methylation reagent, and two methyl groups of the dimethyl sulfate are completely utilized by using different alkali and reaction temperatures in two stages, so that industrial byproducts such as methyl bisulfate, sodium methyl sulfate, potassium methyl sulfate and the like are not generated, the consumption of the dimethyl sulfate is greatly reduced, the production cost is reduced, the pollutant discharge amount is reduced, and the environmental protection treatment difficulty is reduced.
Wherein, in the first stage, the methylation capability of dimethyl sulfate is strong, and the 2, 4-dihydroxybenzophenone can be converted into 2-hydroxy-4-methoxybenzophenone by using strong acid and weak alkali salt and lower temperature.
In the second stage, dimethyl sulfate is completely converted into sodium methyl sulfate, the methylation capacity of the sodium methyl sulfate is weak, and strong alkali and higher reaction temperature are used to convert 2, 4-dihydroxybenzophenone into 2-hydroxy-4-methoxybenzophenone.
2. The invention adopts a two-step method to carry out the reaction, so that methyl in the dimethyl sulfate is fully utilized, the addition amount of the dimethyl sulfate can be effectively reduced, and the reaction components are reduced; and the dimethyl sulfate is completely reacted, no monomethyl sulfate is discharged along with the wastewater, the COD value of the wastewater can be reduced, and sodium sulfate generated after the dimethyl sulfate is completely reacted can be recycled as a byproduct.
3. In the method, the first step is catalyzed by strong acid and weak base salt, only one methyl group of dimethyl sulfate acts, methyl groups in the generated sodium methyl sulfate cannot act, and if the first catalyst adopts strong base, the methylation degree cannot be controlled because the reaction performance is too strong, a large amount of 2, 4-dimethoxy benzophenone impurities can be generated in the system, the methylation degree is out of control, and a large amount of 2, 4-dimethoxy benzophenone is generated. The method comprises the steps of catalyzing by strong acid and weak alkali salt, and adding strong alkali to promote the reaction activity after only sodium methyl sulfate with weak reaction performance remains in the system, so that the sodium methyl sulfate is fully reacted. Through the two-stage reaction, the full utilization of dimethyl sulfate is realized, the consumption of raw materials is reduced, the generation of a large amount of 2, 4-dimethoxy benzophenone is avoided, and the synthesis yield is improved, so that the production cost is reduced to the greatest extent, and the maximization of economic benefit is realized.
4. The waste water in the traditional process is strong in alkalinity, the water body is darker in color, and contains a large amount of sodium methyl sulfate components, the COD reaches more than 10 ten thousand mg/L, the waste water is difficult to directly degrade and treat by double-effect evaporation, and the waste water can be concentrated only by adopting a forced distillation method. The energy consumption in the treatment process is increased sharply, and a large amount of dangerous solid waste sodium methyl sulfate, sodium carbonate and sodium bicarbonate mixed salt are generated simultaneously, so that the environmental protection treatment cost is greatly increased. The process wastewater of the method is weak acid, the color of the water body is light yellow, and the COD is reduced to about 5000 mg/L. The waste water contains only trace sodium methyl sulfate, a small amount of organic matters and sodium sulfate with the concentration of more than 20%, and the sodium sulfate with good appearance and high purity as an industrial byproduct can be obtained through simple decolorization and double-effect evaporation concentration, so that certain economic benefit can be generated.
Drawings
FIG. 1 is a GC diagram for the end of the reaction of example 1:
FIG. 2 is a GC diagram for the end of the reaction of example 2
FIG. 3 is an infrared spectrum of 2-hydroxy-4-methoxybenzophenone of example 6
FIG. 4 is a UV absorption spectrum of 2-hydroxy-4-methoxybenzophenone of example 6
FIG. 5 is a schematic of the crude synthesis scheme in example 6.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1: using a two-stage reaction control effect example, 107.00g (0.499 mol) of crude BP-1, 29.10g (0.275 mol) of sodium carbonate, and 107.00g of cyclohexane were put into a 500ML four-necked flask, and heated by stirring in an oil bath at 65 ℃. The reaction was continued at 62℃with the addition of 36.59g (0.29 mol) of dimethyl sulfate and at 61℃for 30 minutes. The oil bath temperature is set to 95 ℃, the reaction temperature starts to be increased, the material temperature is 81 ℃, and the water diversion reaction is timed for 2 hours. The oil bath was set to 140℃and the desolventizing reaction stage was started. After 2 hours of desolventizing, the cyclohexane is not distilled off at normal pressure; the oil bath temperature was set at 160 ℃. 10.07g (0.102 mol) of 40% sodium hydroxide solution is added, the temperature of the mixture is controlled to be 150-155 ℃ for 2 hours, 100g of water is added, the pH value is adjusted to 5-6 by concentrated sulfuric acid, the mixture is stirred and kept stand for water diversion at 80-85 ℃, and the COD is 5300mg/L by sampling the water phase. The organic phase is subjected to 110 ℃ and normal pressure, then is subjected to decompression and desolventization by a water pump, and is desolventized completely, 113.08g of crude products are collected, GC is sampled, the BP-3 content is 95.42%, the 2, 4-dimethoxy benzophenone content is 2.48%, and the BP-1 content is 0.97%. The yield of the crude product is 99.19%, the content of the crude target product is 95.42%, and the GC diagram is shown in figure 1.
Example 2: the same control conditions as in example 1 were followed, and in the second stage, the effect example was that no sodium hydroxide solution was added,
Into a 500ML four-necked flask, 107.00g (O.499 mol) of crude BP-1, 29.10g (0.275 mol) of sodium carbonate and 107.00g of cyclohexane were charged, and the mixture was heated in an oil bath at 65℃with stirring. The reaction was continued for 30 minutes at 62℃with the addition of 35.95g (0.285 mol) of dimethyl sulfate. The oil bath temperature is set to 95 ℃, the reaction temperature starts to be increased, the material temperature is 81 ℃, and the water diversion reaction is timed for 2 hours. The oil bath was set to 140℃and the desolventizing reaction stage was started. After 1 hour, cyclohexane is not distilled off at normal pressure, and GC, BP-3 content 58.63%, 2, 4-dimethoxy benzophenone content 0.14% and BP-1 content 40.08% are sampled; the oil bath temperature was set at 160 ℃. And (3) adding no 40% sodium hydroxide solution, controlling the temperature of the mixture to be 150-155 ℃ for 2 hours, adding 100g of water, adjusting the pH value to be 5-6 by using concentrated sulfuric acid, controlling the temperature of 80-85 ℃ for stirring, standing and water separation, and sampling an aqueous phase to measure COD to be 43913mg/L. The organic phase is subjected to 110 ℃ and normal pressure, then is subjected to decompression and desolventization by a water pump, 113.23g of crude products are collected after desolventization, the organic phase is sampled, GC, BP-3 content 76.36%, 2, 4-dimethoxy benzophenone content 0.81% and BP-1 content 21.88%. The yield of the crude product is 99.32%, the content of the crude target product is 76.36%, and the GC diagram is shown in figure 2.
Example 3: the reaction solvent is changed into normal hexane, 600g of normal hexane, 79.50g (0.75 mol) of sodium carbonate, 214.00g (0.999 mol) of 2, 4-dihydroxybenzophenone and 88.20g (0.699 mol) of dimethyl sulfate are put into a 2000ML reaction kettle, the temperature of the oil bath is 80 ℃, the reflux water diversion reaction time is 3 hours, then the temperature of the oil bath is 160 ℃, normal pressure is used for distilling the normal hexane in the system, the material temperature reaches 140 ℃, 20.14g (0.201 mol) of 40 percent sodium hydroxide solution is added into the system, and the oil temperature is kept at 160 ℃ for 3 hours. After the reaction is finished, the reaction kettle is cooled to below 100 ℃, 300g of water is pumped into the reaction kettle, the pH value is adjusted to 5-6 by concentrated sulfuric acid, the stirring, standing and water separation are controlled at 80-85 ℃, and the COD is 6543mg/L by sampling the water phase. The organic phase is distilled under reduced pressure at 160℃and vacuum of-0.1 mpa. Desolventizing, collecting 226.48g of crude product, and the yield of the crude product is 99.33%. The desolventized crude product was sampled for GC, BP-3 content 94.85%, 2, 4-dimethoxybenzophenone content 2.13% and BP-1 content 1.39%.
Example 4: 600g of normal hexane, 103.66g (0.75 mol) of potassium carbonate, 214.00g (0.999 mol) of 2, 4-dihydroxybenzophenone and 88.20g (0.699 mol) of dimethyl sulfate are put into a 2000ML reaction kettle, the oil bath temperature is set to 80 ℃, the reflux water diversion reaction time is 3 hours, then the oil bath temperature is set to 160 ℃, normal hexane in the system is distilled out under normal pressure, the material temperature reaches 140 ℃, 20.14g (0.201 mol) of 40 percent sodium hydroxide solution is added into the system, and the oil temperature is kept to 160 ℃ for 3 hours. After the reaction is finished, the reaction kettle is cooled to below 100 ℃,300 g of water is pumped into the reaction kettle, the pH value is adjusted to 5-6 by concentrated sulfuric acid, stirring, standing and water separation are controlled at 80-85 ℃, and COD (chemical oxygen demand) is 4658mg/L by sampling an aqueous phase. The organic phase is distilled under reduced pressure at 160℃and vacuum of-0.1 mpa. Desolventizing, collecting 227.83g of crude product, and the yield of the crude product is 99.92%. The desolventized crude product is sampled to have GC content of 95.12 percent of BP-3, 3.60 percent of 2, 4-dimethoxy benzophenone and 0.51 percent of BP-1.
Example 5: 1000kg of toluene, 205kg of sodium carbonate and 750kg of 2, 4-dihydroxybenzophenone are put into a 3000L reaction kettle, 256kg of dimethyl sulfate is added after stirring and heating to 60 ℃, the temperature is continuously increased to 80-100 ℃ for 1 hour, and then the reflux water diversion reaction is carried out for 1.5 hours after the temperature is increased to more than 110 ℃. Rapidly desolventizing, gradually increasing the steam pressure to the temperature of 140+/-3 ℃ when desolventizing in the kettle. Desolventizing to 140 ℃. 70kg (0.7 kmol) of 40% sodium hydroxide solution is added into the system through a high-level tank, and the steam pressure is controlled to be 0.4-0.5Mpa for 3h of reaction. After the reaction is finished, the temperature is reduced to below 100 ℃, and metered washing water is added into the reaction kettle. The concentrated sulfuric acid is directly pumped into a concentrated sulfuric acid overhead tank and added into a reaction kettle, and the pH of the water phase is controlled between 5 and 6 by the sulfuric acid. When water is separated, the temperature in the kettle is controlled to be 80+/-5 ℃, the water phase is collected in a water separation groove, and the COD (chemical oxygen demand) is measured to be 6840mg/L by sampling the water phase. After water separation, the BP-3 crude product is heated to about 130 ℃ in vacuum to remove toluene and water. Desolventizing, collecting 796.91kg of crude product, and the yield of the crude product is 99.73%. And (3) sampling and detecting crude products at the bottom of the kettle, wherein the content of GC, BP-3 is 96.20%, the content of 2, 4-dimethoxy benzophenone is 2.43% and the content of BP-1 is 0.23%.
Example 6: 1500kg of cyclohexane, 500kg (4.717 kmol) of sodium carbonate, 1500kg (7.002 kmol) of 2, 4-dihydroxybenzophenone and 450kg (3.568 kmol) of dimethyl sulfate are put into a reaction kettle, the reaction temperature is controlled at 75-85 ℃, the reaction time is 3 hours, cyclohexane in the system is distilled out under normal pressure, 70kg (0.7 kmol) of 40% sodium hydroxide solution is added into the system, and then the temperature is raised to 150-160 ℃ and the reaction time is 4 hours. After the reaction is finished, the reaction kettle is cooled to below 100 ℃, 1000kg of water is pumped into the reaction kettle, sulfuric acid is used for controlling the PH of the water phase to be 5-6, water is separated after stirring for 1h, and the upper organic phase slides into the distillation kettle. The organic phase is distilled under reduced pressure in a distillation kettle at 180 ℃ and the vacuum degree is-0.1 mpa. Desolventizing, collecting 1595.41kg of crude product, and the yield of the crude product is 99.83%. Sampling and detecting GC, BP-3 content 95.29%, 2, 4-dimethoxy benzophenone content 3.37% and BP-1 content 0.36%.
Example 7: 2000kg of toluene, 400kg of sodium carbonate, 1500kg (7.002 kmol) of 2, 4-dihydroxybenzophenone and 480kg (3.806 kmol) of dimethyl sulfate are put into a reaction kettle, the reaction temperature is 70-80 ℃, the reaction time is 3 hours, toluene in the system is distilled out under normal pressure, 84kg (0.599 kmol) of 40% potassium hydroxide solution is added into the system, and then the temperature is raised to 160-170 ℃ and the reaction time is 4 hours. After the reaction is finished, the reaction kettle is cooled to below 100 ℃, 1000kg of water is pumped into the reaction kettle, the PH of the water phase is controlled between 5 and 6 by sulfuric acid, water is separated after stirring for 1h, and the upper organic phase slides into the distillation kettle. The organic phase is distilled under reduced pressure in a distillation kettle at 180 ℃ and the vacuum degree is-0.1 mpa. Desolventizing, collecting 1596.21kg of crude product, and the yield of the crude product is 99.88%. Sampling and detecting GC, BP-3 content of 95.12%, 2, 4-dimethoxy benzophenone content of 3.60% and BP-1 content of 0.50%.
The above embodiments are merely preferred embodiments of the present application, and should not be construed as limiting the present application, and the embodiments and features of the embodiments of the present application may be arbitrarily combined with each other without collision. The protection scope of the present application is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this application are also within the scope of the application.
Claims (8)
1. A synthesis process of 2-hydroxy-4-methoxyl diphenyl ketone is characterized in that: 2, 4-dihydroxybenzophenone and dimethyl sulfate are used as raw materials, a first-stage reaction is carried out under the catalysis of a first catalyst in a solvent environment, then a system solvent is distilled out, and a second catalyst is added for a second-stage reaction to prepare 2-hydroxy-4-methoxybenzophenone; wherein the first catalyst is one of potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the reaction temperature is 60-140 ℃; the second catalyst is one of sodium hydroxide and potassium hydroxide, and the reaction temperature is 150-170 ℃; the solvent is one of cyclohexane, toluene and n-heptane.
2. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the reaction time of the first stage is 2-6h.
3. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the reaction time of the second stage is 2-4h.
4. A process for synthesizing 2-hydroxy-4-methoxybenzophenone according to any one of claims 1 to 3, characterized in that: the molar ratio of the 2, 4-dihydroxydiphenyl ketone to the dimethyl sulfate is 1:0.5-0.7.
5. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the mole ratio of the dosage of the first catalyst to the dosage of the 2, 4-dihydroxybenzophenone is 0.5-1: 1.
6. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the molar ratio of the second catalyst to the 2, 4-dihydroxybenzophenone is 0.1-0.5: 1.
7. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the addition amount of the solvent is 1-3 times of the mass of the 2-hydroxy-4-methoxybenzophenone.
8. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: after the second stage reaction is completed, the system is cooled to below 100 ℃, water is added for washing, then the water phase and the organic phase are separated, the organic phase is distilled under reduced pressure to obtain a crude product of 2-hydroxy-4-methoxybenzophenone, and the crude product is recrystallized and refined to obtain the 2-hydroxy-4-methoxybenzophenone product.
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