CN115650836A - Synthesis process of 2-hydroxy-4-methoxybenzophenone - Google Patents
Synthesis process of 2-hydroxy-4-methoxybenzophenone Download PDFInfo
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- methoxybenzophenone
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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 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 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 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002585 base Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 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 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 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
- 238000007670 refining Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 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 10
- 238000004821 distillation Methods 0.000 description 9
- 239000000463 material Substances 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 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000011987 methylation Effects 0.000 description 4
- 238000007069 methylation reaction Methods 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
- 230000008901 benefit Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000012847 fine chemical Substances 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
- 230000009286 beneficial effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption 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-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
- 230000001035 methylating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WBGWGHYJIFOATF-UHFFFAOYSA-M potassium;methyl sulfate Chemical compound [K+].COS([O-])(=O)=O WBGWGHYJIFOATF-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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-methoxybenzophenone, which takes 2, 4-dihydroxy benzophenone and dimethyl sulfate as raw materials and prepares the 2-hydroxy-4-methoxybenzophenone through two-stage catalytic reaction; wherein the catalyst in the first stage is strong base 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 of strong alkali, the consumption of the dimethyl sulfate is reduced, the production cost is reduced, the problem of high discharge amount of COD pollutants in the washing wastewater is solved, and the difficulty in environment-friendly treatment is reduced.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a synthesis process of 2-hydroxy-4-methoxybenzophenone.
Background
2-hydroxy-4-methoxybenzophenone (UV-9) is used as a light stabilizer, can also be used as an intermediate for synthesizing an ultraviolet absorbent 2-hydroxy-4-methoxybenzophenone-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 more and more emphasized in the plastic and rubber industries.
At present, the main method for producing 2-hydroxy-4-methoxybenzophenone at home and abroad is to carry out etherification reaction on 2, 4-dihydroxybenzophenone and dimethyl sulfate, dimethyl sulfate is taken as a methylating reagent, 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, and the method has the defects of mild process conditions, good product quality and high yield, but can generate a large amount of high COD waste (generally accounting for 15 percent of the total mass of the product) such as methyl hydrogen sulfate, sodium methyl sulfate and the like, and is not beneficial to environmental protection treatment, difficult purification and separation, long reaction time and the like (fine chemical intermediates 2010,40 (6): 60-62; fine chemical industry, 2005,22 (2): 142-144).
CN 110128253A discloses that 2, 4-dihydroxy benzophenone and dimethyl carbonate are taken as raw materials to react under the condition of medium temperature and medium pressure, although green and environment-friendly dimethyl carbonate is taken as the raw material, the by-product 2, 4-dimethoxy benzophenone in a reaction system is larger due to poor etherification selectivity, the yield is lower, and the problems of harsh reaction conditions, long reaction time, high cost and the like exist in the technical process.
Therefore, the research and development of a novel preparation process of the 2-hydroxy-4-methoxybenzophenone, which has the advantages of proper cost, high product yield, good quality and high efficiency, has very important significance.
Disclosure of Invention
The invention provides a synthesis process of 2-hydroxy-4-methoxybenzophenone, which can realize the complete utilization of methyl in dimethyl sulfate, reduce the consumption of dimethyl sulfate, reduce the production cost, reduce the pollutant emission and reduce the difficulty of environmental protection treatment.
The technical scheme of the invention is that a synthesis process of 2-hydroxy-4-methoxybenzophenone comprises the steps of carrying out a first-stage reaction by using 2, 4-dihydroxybenzophenone and dimethyl sulfate as raw materials under the catalysis of a first catalyst in a solvent environment, then distilling out a system solvent, and adding a second catalyst to carry out a second-stage reaction to prepare the 2-hydroxy-4-methoxybenzophenone; wherein the first catalyst is strong base 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 second catalyst is one of potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the reaction time of the first stage is 2-6h.
Further, the second catalyst is one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Further, the reaction time of the second stage is 2-4h.
Furthermore, the mol ratio of the 2, 4-dihydroxy benzophenone to the dimethyl sulfate is 1.
Further, the dosage of the first catalyst and the dosage of the 2, 4-dihydroxy benzophenone are 0.5-1: 1.
further, the dosage of the second catalyst and the dosage of the 2, 4-dihydroxy benzophenone are 0.1-0.5: 1.
furthermore, when the reaction raw materials are added, the adopted solvent is one of n-hexane, cyclohexane, toluene and n-heptane, and the adding amount of the solvent is 1-3 times of the mass of the 2-hydroxy-4-methoxybenzophenone.
Further, after the second-stage reaction is finished, cooling the system to below 100 ℃, adding water, mixing uniformly, separating a water phase from an organic phase, carrying out vacuum distillation on the organic phase to obtain a crude product of the 2-hydroxy-4-methoxybenzophenone, and recrystallizing and refining the crude product 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 methylating agent, and different alkalis and reaction temperatures are used in two stages, so that the two methyl groups of dimethyl sulfate are completely utilized, industrial byproducts such as methyl hydrogen sulfate, sodium methyl sulfate, potassium methyl sulfate and the like are not generated, the consumption of 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 2, 4-dihydroxybenzophenone can be converted into 2-hydroxy-4-methoxybenzophenone by using strong acid, weak base salt and lower temperature.
In the second stage, dimethyl sulfate is completely converted into sodium methyl sulfate, the methylation capability of the sodium methyl sulfate is weak, and 2, 4-dihydroxy benzophenone can be converted into 2-hydroxy-4-methoxybenzophenone only by using strong alkali and higher reaction temperature.
2. According to the invention, because a two-step method is adopted for reaction, methyl in dimethyl sulfate is fully utilized, the addition amount of dimethyl sulfate can be effectively reduced, and 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 the sodium sulfate generated after the dimethyl sulfate is completely reacted can also be recycled as a byproduct.
3. In the first step of the method, strong acid and weak base salt are used for catalysis, only one methyl group of dimethyl sulfate plays a role, and the methyl group in the generated sodium methyl sulfate does not play a role, if the first catalyst adopts strong base, a large amount of 2, 4-dimethoxy benzophenone impurities can be generated in the system due to too strong reaction performance and uncontrollable methylation degree, so that the methylation degree is out of control, and a large amount of 2, 4-dimethoxy benzophenone is generated. The method firstly uses strong acid and weak base salt for catalysis, and after only sodium methyl sulfate with weak reaction performance remains in the system, strong base is added to improve the reaction activity, so that the sodium methyl sulfate is completely reacted. Through the reaction of two stages, the complete utilization of dimethyl sulfate is realized, the raw material consumption 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 maximum degree, and the maximization of economic benefit is realized.
4. The wastewater in the traditional process is strongly alkaline, the water body is dark in color, and contains a large amount of sodium methyl sulfate components, COD (chemical oxygen demand) reaches more than 10 ten thousand mg/L, the wastewater is difficult to directly degrade and is treated by double-effect evaporation, and only a forced distillation method is adopted for concentration. The energy consumption is increased sharply in the treatment process, and simultaneously, a large amount of toxic dangerous solid waste mixed salt of the methyl sulfate sodium, the sodium carbonate and the sodium bicarbonate is generated, so that the environmental protection treatment cost is greatly increased. The process wastewater of the method is faintly acid, the color of the water body is light yellow, and the COD is reduced to about 5000 mg/L. The wastewater only contains trace sodium methyl sulfate, a small amount of organic matters and more than 20 percent of sodium sulfate, and the high-purity industrial byproduct sodium sulfate with better appearance can be obtained by simple decoloration and double-effect evaporation concentration, so that certain economic benefit can be generated.
Drawings
FIG. 1 is the GC spectrum at the end of the reaction of example 1:
FIG. 2 is GC-map of the end of reaction in example 2
FIG. 3 is an IR spectrum of 2-hydroxy-4-methoxybenzophenone in example 6
FIG. 4 is a chart of UV absorption spectrum of 2-hydroxy-4-methoxybenzophenone in example 6
FIG. 5 is a schematic diagram 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 illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1: using the 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 in a 500ML four-necked flask, and the flask was put in an oil bath at 65 ℃ and heated with stirring. At the material temperature of 62 ℃, 36.59g (0.29 mol) of dimethyl sulfate is added, the material temperature is stabilized at 61 ℃, and the reaction is carried out for 30 minutes. Setting the oil bath temperature to be 95 ℃, starting to increase the reaction temperature, keeping the material temperature to be 81 ℃, and timing the water diversion reaction for 2 hours. The oil bath was set to 140 ℃ and the desolventizing reaction phase was started. After desolventizing for 2 hours, cyclohexane is not distilled off under normal pressure; the oil bath temperature was set at 160 ℃. Adding 10.07g (0.102 mol) of 40% sodium hydroxide solution, controlling the material temperature at 150-155 ℃ for reaction for 2h, adding 100g of water, adjusting the pH value to 5-6 by concentrated sulfuric acid, stirring and standing at 80-85 ℃ for water diversion, and sampling the water phase to measure that the COD is 5300mg/L. And (3) desolventizing the organic phase at 110 ℃ under normal pressure and then using a water pump to remove the solvent completely, collecting 113.08g of crude product, and sampling GC, wherein 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 crude yield is 99.19%, the content of the crude target product is 95.42%, and the GC pattern is shown in figure 1.
Example 2: the same control conditions as in example 1, without adding sodium hydroxide solution in the second stage,
107.00g (O.499mol) of crude BP-1, 29.10g (0.275 mol) of sodium carbonate and 107.00g of cyclohexane are put into a 500ML four-neck bottle, and the bottle is put into an oil bath at 65 ℃ and stirred and heated. At a material temperature of 62 ℃, 35.95g (0.285 mol) of dimethyl sulfate is added for reaction for 30 minutes. Setting the oil bath temperature to be 95 ℃, starting to increase the reaction temperature, keeping the material temperature to be 81 ℃, and timing the water diversion reaction for 2 hours. The oil bath was set to 140 ℃ and the desolventizing reaction phase was started. After 1 hour, cyclohexane is not distilled off under normal pressure, and GC is sampled, wherein the content of BP-3 is 58.63 percent, the content of 2, 4-dimethoxy benzophenone is 0.14 percent, and the content of BP-1 is 40.08 percent; the oil bath temperature was set at 160 ℃. Adding no 40% sodium hydroxide solution, controlling the material temperature at 150-155 deg.C, reacting for 2 hr, adding 100g water, adjusting pH to 5-6 with concentrated sulfuric acid, stirring at 80-85 deg.C, standing for water separation, and sampling water phase to obtain COD of 43913mg/L. The organic phase is subjected to pressure reduction desolventizing at 110 ℃ and then is subjected to pressure reduction by a water pump, 113.23g of crude product is collected, and GC is sampled from the organic phase, wherein the content of BP-3 is 76.36%, the content of 2, 4-dimethoxy benzophenone is 0.81%, and the content of BP-1 is 21.88%. The crude product yield is 99.32%, the content of the crude target product is 76.36%, and the GC pattern is shown in figure 2.
Example 3: the reaction solvent is changed into n-hexane, 600g of n-hexane, 79.50g (0.75 mol) of sodium carbonate, 214.00g (0.999 mol) of 2, 4-dihydroxy benzophenone and 88.20g (0.699 mol) of dimethyl sulfate are put into a 2000ML reaction kettle, the oil bath temperature is set to be 80 ℃, the reflux and water diversion reaction time is 3 hours, then the oil bath temperature is set to be 160 ℃, the n-hexane in the system is evaporated under normal pressure, 20.14g (0.201 mol) of 40% sodium hydroxide solution is added into the system when the material temperature reaches 140 ℃, and the reaction time is 3 hours under the oil temperature of 160 ℃. After the reaction is finished, the temperature of the reaction kettle is reduced to be below 100 ℃, 300g of water is pumped into the reaction kettle, the pH value is adjusted to be 5-6 by concentrated sulfuric acid, the mixture is stirred and kept stand for water diversion at the temperature of 80-85 ℃, and the COD measured by sampling the water phase is 6543mg/L. The organic phase is distilled under reduced pressure, the distillation temperature is 160 ℃, and the vacuum degree is-0.1 mpa. After desolventizing, 226.48g of crude product is collected, and the yield of the crude product is 99.33%. GC is taken as a sample of the desolventizing crude product, and the content of BP-3 is 94.85 percent, the content of 2, 4-dimethoxy benzophenone is 2.13 percent, and the content of BP-1 is 1.39 percent.
Example 4: 600g of n-hexane, 103.66g (0.75 mol) of potassium carbonate, 214.00g (0.999 mol) of 2, 4-dihydroxy benzophenone and 88.20g (0.699 mol) of dimethyl sulfate are put into a 2000ML reaction kettle, the oil bath temperature is set to be 80 ℃, the reflux water diversion reaction time is 3 hours, then the oil bath temperature is set to be 160 ℃, the n-hexane in the system is evaporated under normal pressure, 20.14g (0.201 mol) of 40% sodium hydroxide solution is added into the system when the material temperature reaches 140 ℃, and the oil temperature is kept to be 160 ℃ for the reaction time to be 3 hours. After the reaction is finished, the temperature of the reaction kettle is reduced to be below 100 ℃, 300g of water is pumped into the reaction kettle, the pH value is adjusted to be 5-6 by concentrated sulfuric acid, the mixture is stirred and kept stand for water diversion at the temperature of 80-85 ℃, and the COD measured by sampling the water phase is 4658mg/L. The organic phase is distilled under reduced pressure, the distillation temperature is 160 ℃, and the vacuum degree is-0.1 mpa. And (4) desolventizing completely, collecting 227.83g of crude product, and obtaining 99.92% of crude product yield. GC is taken as a sample of the desolventizing crude product, and the content of BP-3 is 95.12 percent, the content of 2, 4-dimethoxy benzophenone is 3.60 percent, and the content of BP-1 is 0.51 percent.
Example 5: 1000kg of toluene, 205kg of sodium carbonate and 750kg of 2, 4-dihydroxy benzophenone are put into a 3000L reaction kettle, stirred and heated to 60 ℃, then 256kg of dimethyl sulfate is added, the temperature is continuously raised to 80-100 ℃ for 1 hour, and then the temperature is raised to more than 110 ℃ for reflux and water diversion reaction for 1.5 hours. And (3) quickly desolventizing, gradually increasing the steam pressure to desolventize until the temperature in the kettle is 140 +/-3 ℃. Desolventizing to 140 ℃. 70kg (0.7 kmol) of 40% sodium hydroxide solution is added into the system through a head tank, and the steam pressure is controlled to be 0.4-0.5Mpa for reaction for 3 hours. After the reaction is finished, cooling to below 100 ℃, and adding metered washing water into the reaction kettle. The concentrated sulfuric acid is directly pumped into a concentrated sulfuric acid head tank and added into a reaction kettle, and the pH of the aqueous phase is controlled between 5 and 6 by the sulfuric acid. The temperature in the kettle is controlled to be 80 +/-5 ℃ during water diversion, the water phase is collected in a water diversion tank, and COD is measured by sampling the water phase to be 6840mg/L. After the water is distributed, the crude BP-3 product is heated to 130 ℃ in vacuum to remove toluene and water. After desolventizing, 796.91kg of crude product is collected, and the yield of the crude product is 99.73%. The crude product at the bottom of the kettle is sampled and detected by GC, and the content of BP-3 is 96.20 percent, the content of 2, 4-dimethoxy benzophenone is 2.43 percent, and the content of BP-1 is 0.23 percent.
Example 6: 1500kg of cyclohexane, 500kg of sodium carbonate (4.717 kmol), 1500kg of 2, 4-dihydroxy benzophenone (7.002 kmol) and 450kg of dimethyl sulfate (3.568 kmol) are put into a reaction kettle, the reaction temperature is controlled to be 75-85 ℃, the reaction time is 3 hours, the cyclohexane in the system is evaporated under normal pressure, 70kg of 40% sodium hydroxide solution (0.7 kmol) is added into the system, then the temperature is raised to 150-160 ℃, and the reaction time is 4 hours. After the reaction is finished, the temperature of the reaction kettle is reduced to be below 100 ℃, 1000kg of water is pumped into the reaction kettle, the pH of the water phase is controlled by sulfuric acid to be between 5 and 6, the water is divided after stirring for 1 hour, and the upper organic phase is distilled into a distillation kettle. The organic phase is distilled under reduced pressure in a distillation kettle, the distillation temperature is 180 ℃, and the vacuum degree is-0.1 mpa. Exsolution is completed, crude product 1595.41kg is collected, and the yield of the crude product is 99.83%. Sampling and detecting GC, the BP-3 content is 95.29 percent, the 2, 4-dimethoxy benzophenone content is 3.37 percent, and the BP-1 content is 0.36 percent.
Example 7: 2000kg of toluene, 400kg of sodium carbonate, 1500kg (7.002 kmol) of 2, 4-dihydroxy benzophenone 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 a system is evaporated 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 temperature of the reaction kettle is reduced to be below 100 ℃, 1000kg of water is pumped into the reaction kettle, the pH of the water phase is controlled to be between 5 and 6 by sulfuric acid, water is divided after stirring for 1 hour, and the upper organic phase is distilled into a distillation kettle. The organic phase is distilled under reduced pressure in a distillation kettle, the distillation temperature is 180 ℃, and the vacuum degree is-0.1 mpa. Exsolution is completed, crude product 1596.21kg is collected, and the yield of the crude product is 99.88%. Sampling and detecting GC, wherein the BP-3 content is 95.12 percent, the 2, 4-dimethoxy benzophenone content is 3.60 percent, and the BP-1 content is 0.50 percent.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. A synthesis process of 2-hydroxy-4-methoxybenzophenone is characterized by comprising the following steps: taking 2, 4-dihydroxy benzophenone and dimethyl sulfate as raw materials, carrying out a first-stage reaction under the catalysis of a first catalyst in a solvent environment, then evaporating a system solvent, adding a second catalyst to carry out a second-stage reaction to prepare 2-hydroxy-4-methoxybenzophenone; wherein the first catalyst is strong base weak acid salt, and the reaction temperature is 60-140 ℃; the second catalyst is strong alkali, and the reaction temperature is 150-170 ℃.
2. The process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: the first catalyst is one of potassium carbonate, sodium bicarbonate and potassium bicarbonate.
3. The process of claim 2 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: the reaction time of the first stage is 2-6h.
4. The process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: the second catalyst is one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
5. The process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: the reaction time of the second stage is 2-4h.
6. The process for synthesizing 2-hydroxy-4-methoxybenzophenone according to any one of claims 1 to 5, wherein: the mol ratio of the 2, 4-dihydroxy benzophenone to the dimethyl sulfate is 1:0.5-0.7.
7. The process for the synthesis of 2-hydroxy-4-methoxybenzophenone according to claim 1, wherein: the dosage of the first catalyst and the dosage of the 2, 4-dihydroxybenzophenone are 0.5 to 1:1.
8. the process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: the dosage of the second catalyst and the dosage of the 2, 4-dihydroxy benzophenone are 0.1 to 0.5:1.
9. the process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: when the reaction raw materials are added, the adopted solvent is one of n-hexane, cyclohexane, toluene and n-heptane, and the adding amount of the solvent is 1 to 3 times of the mass of the 2-hydroxy-4-methoxybenzophenone.
10. The process of claim 1 for the synthesis of 2-hydroxy-4-methoxybenzophenone, wherein: after the second stage reaction is finished, cooling the system to below 100 ℃, adding water for washing, separating a water phase from an organic phase, carrying out vacuum distillation on the organic phase to obtain a crude product of the 2-hydroxy-4-methoxybenzophenone, and recrystallizing and refining the crude product to obtain the 2-hydroxy-4-methoxybenzophenone product.
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