CN107879910B - Green synthesis process of 2, 4-dihydroxy benzophenone - Google Patents
Green synthesis process of 2, 4-dihydroxy benzophenone Download PDFInfo
- Publication number
- CN107879910B CN107879910B CN201711061208.4A CN201711061208A CN107879910B CN 107879910 B CN107879910 B CN 107879910B CN 201711061208 A CN201711061208 A CN 201711061208A CN 107879910 B CN107879910 B CN 107879910B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dihydroxy benzophenone
- saturated solution
- reaction
- hzsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims description 4
- 238000003786 synthesis reaction Methods 0.000 title claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000012047 saturated solution Substances 0.000 claims abstract description 36
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 235000019441 ethanol Nutrition 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 239000002250 absorbent Substances 0.000 abstract description 6
- 230000002745 absorbent Effects 0.000 abstract description 6
- 231100000053 low toxicity Toxicity 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 239000012461 cellulose resin Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000004611 light stabiliser Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 2
- 239000005061 synthetic rubber Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 238000005917 acylation reaction Methods 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000010933 acylation Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- -1 2, 4-dihydroxy-toluene ketone Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 2
- FNYDIAAMUCQQDE-UHFFFAOYSA-N 3-hydroxy-4-methylphenol Natural products CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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 belongs to the field of fine chemical engineering, and discloses a new process for synthesizing a 2, 4-dihydroxy benzophenone ultraviolet absorbent. The method comprises the following steps: adding an ethanol saturated solution of resorcinol and a certain amount of catalyst BiCl into a reaction vessel3Or doped with 5% (w/w) CeO2The compound HZSM-5 zeolite catalyst is prepared by dropwise adding an ethanol saturated solution of benzoic anhydride under good stirring, carrying out reflux reaction at 60-80 ℃ for a certain time, and then stopping heating to separate out solid substances. And performing subsequent treatment according to different selected catalysts, separating the catalyst from a crude product, and recrystallizing the crude product by adopting a mixed solution of ethanol and water to obtain a finished product of the 2, 4-dihydroxy benzophenone. The invention uses low-toxicity and low-harm raw materials and reagents, adopts a novel catalyst which has the characteristics of easy separation and easy recovery, has simple process and little environmental pollution in the whole reaction process, and ensures that the purity of the synthesized 2, 4-dihydroxy benzophenone reaches more than 99 percent and the yield reaches more than 94 percent. It is suitable for use as light stabilizer for polyvinyl chloride, polystyrene, epoxy resin, cellulose resin, unsaturated resin, paint and synthetic rubber.
Description
Technical Field
The invention belongs to the field of fine organic chemical industry, and particularly relates to a new process for synthesizing a 2, 4-dihydroxy benzophenone ultraviolet absorbent.
Background
The ultraviolet absorbent can absorb the sunlight and the ultraviolet part in the fluorescent light source, and solves the problem of fading of the product surface. Research and development of novel electronic chemicals such as ultraviolet absorbers and photoresists have become a focus of recent attention in the fine chemical industry at home and abroad. 2,4 dihydroxy benzophenone is a high-efficient ultraviolet absorbent, also called UV-O, and belongs to a series of products of benzophenone ultraviolet absorbent, and because of better comprehensive performance, low price and wide application range, the benzophenone plays an important role in the ultraviolet absorbent, and is widely applied to a plurality of fields of polymer materials, coatings (automobile spray painting and building finishing), printing ink, post-treatment of dyed/printed textiles, sun-screening cosmetics and the like. Can also be used as an intermediate for synthesizing other ultraviolet absorbers, and has the structure:
the following are the relevant documents and the current state of the art in recent years relating to the synthesis of 2, 4-dihydroxybenzophenone:
a preparation method of 2, 4-dihydroxy benzophenone, which is a patent issued in 5 months of 2010 by Li Xiaolin, Hu Lin Song and the like, and CN 101830791A introduces a preparation method of taking trichlorotoluene and resorcinol as raw materials and esters as catalysts. The method has simple process, safe operation and higher product yield and purity, but the used trichlorotoluene belongs to toxic, harmful and unstable raw materials, and a large amount of HCl acid mist and harmful wastewater are generated by hydrolysis, so that the method causes corrosion to equipment and increases the cost of subsequent environment-friendly treatment.
Wu, Yajuan and the like, in 2015, 4 months, reported in the proceedings of Chongqing academy of science and technology, introduced a preparation process of 2, 4-dihydroxybenzophenone by using benzoic acid and resorcinol as raw materials and indium trichloride as a catalyst. The benzoic acid used as the raw material in the method is easy to sublimate and is adhered to the wall of the reactor, and the benzoic acid has lower activity as an acylation reagent, long reaction time, high production and operation cost and difficult operation of discharging the melt. In addition, Lewis acid such as aluminum trichloride and the like is generally adopted in the industry as a catalyst, and toxic and harmful benzoyl chloride is used as an acylation reagent to prepare 2, 4-dihydroxy benzophenone, so that the problem of HCl acid mist is also generally existed. AlCl3Easy to complex with the product to generate by-products and reduce the yield. To eliminate its effect, water and AlCl are often added3Hydrolysis reaction occurs, but then HCl acid mist and waste water and gas emission problems, equipment corrosion and the like are generated.
The invention adopts the resorcinol and the benzoic anhydride with low toxicity and low harm as reaction raw materials, has little threat to health and environment, and the benzoic anhydride is taken as an acylation reaction reagent, has stronger activity than benzoic acid, thereby the efficiency of preparing the 2, 4-dihydroxy-toluene ketone is high, and the production cost is low. HCl acid mist is not generated in the reaction process, the problems of waste water and waste gas emission and equipment corrosion of a factory are solved, equipment and process investment caused by tail gas treatment is saved, and the production cost is greatly reduced.
At the same time, the invention selects BiCl3And zeolite catalyst instead of common acylation catalyst AlCl3Not only avoid AlCl3By-products generated by complexing with the product are avoided, and AlCl is also avoided3Difficult to recycleAnd (5) problems are solved. The selected novel catalyst solves the problems of difficult recovery, serious pollution and difficult subsequent treatment caused by the traditional catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 4-dihydroxy benzophenone, which overcomes the defects of the prior art.
The preparation method of the 2, 4-dihydroxy benzophenone comprises the following steps:
(1) weighing a proper amount of resorcinol, dissolving the resorcinol in absolute ethyl alcohol to prepare a saturated solution a at 60 ℃, weighing a proper amount of benzoic anhydride, dissolving the benzoic anhydride in the absolute ethyl alcohol to prepare a saturated solution b at 60 ℃, and weighing a proper amount of catalyst.
(2) Adding catalyst BiCl into a reactor3Or doped with 5% (w/w) CeO2Stirring the HZSM-5 zeolite catalyst and the saturated solution a, dropwise adding the saturated solution b into the mixture, and fully reacting for 2.5 to 4.5 hours at the temperature of between 60 and 80 ℃.
(3) If the catalyst is selected from BiCl3: and after the reaction is finished, cooling to 0-15 ℃, separating out a solid, obtaining a crude product of the 2, 4-dihydroxybenzophenone from the filtered filter residue, then recrystallizing and refining by using a mixed solvent of ethanol and water =4:1 (volume ratio, the same below), and drying to obtain a finished product of the 2, 4-dihydroxybenzophenone.
(4) If the catalyst is selectively doped with 5% (w/w) CeO2HZSM-5 zeolite catalyst of (1): after the reaction is finished, cooling to 0-15 ℃, and filtering to obtain filter residue doped with 5% (w/w) CeO2Dissolving the solid mixture of the HZSM-5 zeolite catalyst and the 2, 4-dihydroxy benzophenone in acetone, filtering, recovering the obtained filter residue to obtain the zeolite catalyst for recycling, evaporating the filtrate to obtain acetone for recycling, remaining to obtain a crude product of the 2, 4-dihydroxy benzophenone, recrystallizing and refining by using a mixed solvent of ethanol and water =4:1 (volume ratio), and drying to obtain a finished product of the 2, 4-dihydroxy benzophenone.
Doped with 5% (w/w) CeO2The preparation method of the HZSM-5 zeolite catalyst comprises the following steps: weighing 0.5gCeO2And 9.5g of zeolite molecular sieve are put in a crucible, mixed evenly and placed at 500-550 DEG CBaking in a muffle furnace to obtain the product doped with 5% (w/w) CeO2The HZSM-5 zeolite catalyst.
According to the reaction involved in step (2) is:
in a preferable scheme, in the step (1), a proper amount of resorcinol is weighed and dissolved in absolute ethyl alcohol to prepare a saturated solution a at 60 ℃, and a proper amount of benzoic anhydride is weighed and dissolved in absolute ethyl alcohol to prepare a saturated solution b at 60 ℃. Therefore, the resorcinol and the benzoic anhydride can achieve high solubility, the concentration of reactants is high, and the reaction rate is favorably improved.
In the step (1), anhydrous ethanol is selected as a reaction solvent to facilitate the subsequent separation of products, and a catalyst BiCl is avoided3The problem of large amounts of hydrogen chloride produced by hydrolysis, the hydrolysis equation: BiCl3+H2O=BiOCl+2HCl
The catalyst selected in the step (1) can be: BiCl3Or doped with 5% (w/w) CeO2One of the HZSM-5 zeolite catalysts of (1). Selects a novel catalyst to replace the common catalyst AlCl for acylation reaction3Avoid AlCl3By-products generated by complexing with other substances are avoided, and AlCl is also avoided3Difficult to recycle.
If BiCl is selected3As a catalyst, after the reaction is finished, cooling the reaction system to 0-15 ℃, separating out solid substances, washing filter residue I after filtration by using cold ethanol to obtain a crude product of 2, 4-dihydroxy benzophenone, recrystallizing the crude product by using a mixed solvent of ethanol and water =4:1 (volume ratio) to obtain a refined product, and drying to obtain a finished product of 2, 4-dihydroxy benzophenone; evaporating the filtered filtrate and the ethanol washing liquid after washing the filter residue, recycling the ethanol solvent, and taking the solid separated out after evaporating the ethanol as a catalyst BiCl3The mixture with a small amount of raw materials can be reserved for the next experiment to be used as a catalyst containing a small amount of raw materials for recycling, and the effect of catalytic reaction is not influenced.
If optional, 5% (w/w) CeO2HZSM-5 zeolite catalyst of (1): and after the reaction is finished, cooling the reaction system to 0-15 ℃, separating out a solid mixture of the zeolite catalyst and the product, and filtering to obtain filter residue I (the solid mixture I of the zeolite catalyst and the product). Washing with a certain amount of acetone, filtering to obtain filtrate and filter residue II, respectively, evaporating the acetone from the filtrate to obtain crude 2, 4-dihydroxybenzophenone, recrystallizing the crude product with a mixed solvent of ethanol and water =4:1 (volume ratio) to obtain a refined wet product, and drying to obtain a finished product of 2, 4-dihydroxybenzophenone; washing with acetone, filtering to obtain residue II, and oven drying to obtain recovered CeO-containing extract2The compound HZSM-5 zeolite catalyst can be recycled.
The mass of the catalyst in the step (1) accounts for 1-5%, preferably 2-4% of the mass of the sum of the benzoic anhydride and the resorcinol.
In the step (1), the molar ratio of the benzoic anhydride to the resorcinol is 1 (1.6-2.0), preferably 1 (1.85-1.95). As is apparent from the chemical reaction formula, benzoic anhydride and resorcinol react at a ratio of 1:2, and in this reaction, it is preferable to weigh the benzoic anhydride in an excess amount to allow the resorcinol to react sufficiently.
In the step (2), the stirring speed of the reaction system is 300-400 rpm, and under the condition, the materials are ensured to be fully contacted and reacted.
In the step (2), the reaction temperature is controlled to be 60-80 ℃, and preferably 70-80 ℃. Experiments prove that the reaction has the highest activity and the highest conversion rate at the temperature of 70-80 ℃.
In the step (2), the reaction time is controlled to be 2.5-4.5 hours, preferably 3-4 hours. When the reaction time is less than 2.5 hours, most of reactants are not completely reacted, the reaction is not completely carried out, and the reaction efficiency is not high; when the reaction time is longer than 4.5 hours, the yield of the reaction is rarely increased, and the time cost is increased.
In the step (3), the organic solvent selected for recrystallization is a mixed solvent of ethanol and water, the ratio of ethanol to water is 4:1 (volume ratio, the same applies below), and organic impurities and a main byproduct xanthone in the reaction can be removed by the treatment.
The core of the invention is to synthesize the 2, 4-dihydroxy benzophenone by a green method by selecting a low-toxicity and low-harm acylation reagent and a novel catalyst which is high in efficiency and easy to recover.
The method for preparing 2, 4-dihydroxy toluene ketone provided by the invention has the following advantages and obvious technical progress and economic effect:
1. the invention adopts the resorcinol and the benzoic anhydride with low toxicity and low harm as reaction raw materials, has little threat to health and environment, does not generate HCl acid mist in the reaction process, solves the problems of waste water and waste gas emission and equipment corrosion of factories, saves equipment and process investment caused by tail gas treatment, and greatly reduces the production cost.
2. The invention selects BiCl3And zeolite catalyst instead of common acylation catalyst AlCl3Not only avoid AlCl3By-products are generated by complexing with the product, and AlCl is also avoided3Difficult to recycle. The selected novel catalyst solves the problems of difficult recovery, serious pollution and difficult subsequent treatment caused by the traditional catalyst.
3. The invention adopts benzoic anhydride as an acylation reaction reagent, and the activity of the acylation reaction reagent is stronger than that of benzoic acid, so that the 2, 4-dihydroxy-xylene ketone is prepared with high efficiency and low production cost.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1:
1.76g of resorcinol, 2.26g of benzoic anhydride and 0.16g of BiCl were weighed out3. Dissolving resorcinol in ethanol at room temperature to prepare a saturated solution a at 60 ℃, and dissolving benzoic anhydride in ethanol to prepare a saturated solution b at 60 ℃. BiCl3And the saturated solution a was placed in a reactor, stirred and the saturated solution b was added dropwise thereto, and reacted sufficiently at 73 ℃ for 4 hours. Cooling to 5 deg.C after reaction, filtering, recrystallizing the residue with organic solvent (volume ratio of ethanol to water =4: 1), oven drying, and weighing3.23g, the content of 2, 4-dihydroxy benzophenone is 99.45 percent by HPLC detection, and the yield is 94.42 percent.
Example 2:
weighing 2.03g of resorcinol, 2.26g of benzoic anhydride and 0.17g of BiCl3. Dissolving resorcinol in ethanol at room temperature to prepare a saturated solution a at 60 ℃, and dissolving benzoic anhydride in ethanol to prepare a saturated solution b at 60 ℃. BiCl3And the saturated solution a is placed in a reactor, stirred, and the saturated solution b is added dropwise, and the temperature is kept at 73 ℃ for full reaction for 4 hours. After the reaction, the reaction mixture was cooled to 5 ℃, filtered, and the residue was recrystallized and purified using an organic solvent of ethanol/water =4:1, and then dried and weighed 3.75g, and the content of 2, 4-dihydroxybenzophenone was 99.38% by HPLC, and the yield was 94.63%.
Example 3:
weighing 2.20g of resorcinol, 2.260 g of benzoic anhydride, and 0.22g of BiCl3. Dissolving resorcinol in ethanol at 60 deg.C to obtain saturated solution a, and dissolving benzoic anhydride in ethanol to obtain saturated solution b at 60 deg.C. BiCl3And the saturated solution a was placed in a reactor, stirred and the saturated solution b was added dropwise thereto, and reacted sufficiently at 73 ℃ for 4 hours. After the reaction, the reaction mixture was cooled to 5 ℃, filtered, and the residue was recrystallized from an organic solvent of ethanol/water =4:1, dried and weighed 4.03g, and the content of 2, 4-dihydroxybenzophenone was 99.20% by HPLC, and the yield was 94.22%.
Example 4:
weighing 1.76g of resorcinol, 2.26g of benzoic anhydride, doped with 5% (w/w) CeO20.16g of HZSM-5 zeolite catalyst. Dissolving resorcinol in ethanol at 60 deg.C to obtain saturated solution a, and dissolving benzoic anhydride in ethanol to obtain saturated solution b at 60 deg.C. Adding 5% (w/w) CeO2The HZSM-5 zeolite catalyst and the saturated solution a were placed in a reactor, stirred and the saturated solution b was added dropwise thereto, followed by a full reaction at 73 ℃ for 4 hours. After the reaction is finished, cooling to 15 ℃, filtering, and obtaining the mixture doped with 5% (w/w) CeO in the filter residue2Dissolving the mixture of HZSM-5 zeolite catalyst and 2, 4-dihydroxy benzophenone in acetone, filtering, and recovering the filter residueA recycled catalyst; distilling the filtrate at 60 ℃ to recover acetone to obtain a crude product of 2, 4-dihydroxybenzophenone, recrystallizing and refining the crude product with an organic solvent of ethanol and water =4:1, drying the refined product, weighing 3.30g, and detecting the content of 2, 4-dihydroxybenzophenone by HPLC (high performance liquid chromatography) to be 99.70% and the yield to be 96.33%.
Example 5:
0.16g of HZSM-5 zeolite catalyst doped with 5% (w/w) CeO2 was weighed in 2.03g of resorcinol, 2.26g of benzoic anhydride. Dissolving resorcinol in ethanol at 60 deg.C to obtain saturated solution a, and dissolving benzoic anhydride in ethanol to obtain saturated solution b at 60 deg.C. Adding 5% (w/w) CeO2The HZSM-5 zeolite catalyst and the saturated solution a were placed in a reactor, stirred and the saturated solution b was added dropwise thereto, followed by a full reaction at 73 ℃ for 4 hours. After the reaction is finished, cooling to 5 ℃, filtering, and obtaining the mixture doped with 5% (w/w) CeO in the filter residue2Dissolving the mixture of the HZSM-5 zeolite catalyst and the 2, 4-dihydroxy benzophenone in acetone, filtering, and recovering filter residues to obtain the catalyst capable of being recycled; distilling the filtrate at 60 ℃ to recover acetone to obtain a crude product of the 2, 4-dihydroxybenzophenone, recrystallizing and refining the crude product by using an organic solvent of ethanol and water =4:1, drying the crude product, weighing 3.82g, detecting the content of the 2, 4-dihydroxybenzophenone by HPLC (high performance liquid chromatography) to be 99.70 percent, and obtaining the yield of 96.58 percent.
Example 6:
weighing 2.20g of resorcinol, 2.26g of benzoic anhydride, doped with 5% (w/w) CeO20.16g of HZSM-5 zeolite catalyst. Dissolving resorcinol in ethanol at 60 deg.C to obtain saturated solution a, and dissolving benzoic anhydride in ethanol to obtain saturated solution b at 60 deg.C. Adding 5% (w/w) CeO2The HZSM-5 zeolite catalyst and the saturated solution a were placed in a reactor, stirred and the saturated solution b was added dropwise thereto, followed by a full reaction at 73 ℃ for 4 hours. After the reaction is finished, cooling to 5 ℃, filtering, and obtaining the mixture doped with 5% (w/w) CeO in the filter residue2Dissolving the mixture of the HZSM-5 zeolite catalyst and the 2, 4-dihydroxy benzophenone in acetone, filtering, and recovering filter residues to obtain the catalyst capable of being recycled; distilling the filtrate at 60 deg.C to recover acetone to obtain 2, 4-dihydroxy benzophenoneAnd recrystallizing the crude product by using an organic solvent with the ratio of ethanol to water =4:1, drying, weighing 4.13g, detecting the content of the 2, 4-dihydroxy benzophenone by HPLC (high performance liquid chromatography) to be 99.70%, and obtaining the yield of 96.51%. Examples 1-6 the results of the experiments are given in table 1 below.
TABLE 1 Experimental results of examples 1-6
According to the experimental example, the invention has low cost and simple operation, the raw materials and the reaction solvent selected by the provided preparation route of the 2, 4-dihydroxy benzophenone are benzoic anhydride and ethanol with low toxicity and low harm, the benzoic anhydride is used as an acylation reaction reagent, the activity of the benzoic anhydride is stronger than that of benzoic acid, and therefore, the efficiency of preparing the 2, 4-dihydroxy xylene ketone is high, and the production cost is low. Selects a novel catalyst to replace anhydrous AlCl which is difficult to separate and easy to produce byproducts3The method reduces the threat to the environment and the health of the body, solves the pollution problem in enterprises, saves the equipment and process investment caused by tail gas treatment, and provides a new environment-friendly, efficient and green process for synthesizing the 2, 4-dihydroxy benzophenone. The prepared 2, 4-dihydroxy benzophenone product is suitable for being used as a light stabilizer of polyvinyl chloride, polystyrene, epoxy resin, cellulose resin, unsaturated resin, paint and synthetic rubber.
Claims (3)
1. A synthesis process of 2, 4-dihydroxy benzophenone is characterized by comprising the following steps:
(1) weighing a proper amount of resorcinol, dissolving the resorcinol in absolute ethyl alcohol to prepare a saturated solution a at the temperature of 60 ℃, weighing a proper amount of benzoic anhydride, dissolving the benzoic anhydride in the absolute ethyl alcohol to prepare a saturated solution b at the temperature of 60 ℃, and weighing a proper amount of catalyst;
(2) adding catalyst BiCl into a reactor3Or HZSM-5 zeolite catalyst doped with 5% (w/w) CeO2, saturated solution a, stirring, dropwise adding saturated solution b, and reacting at 60-80 deg.C for 2.5
-4.5 hours;
(3) if the catalyst is BiCl3, cooling to 0-15 ℃ after the reaction is finished, filtering to obtain a crude product of 2, 4-dihydroxy benzophenone, recrystallizing and refining by using a mixed solvent of ethanol and water =4:1, and drying to obtain a finished product of 2, 4-dihydroxy benzophenone;
(4) if the catalyst was selected to be an HZSM-5 zeolite catalyst doped with 5% (w/w) CeO 2: after the reaction is finished, cooling to 0-15 ℃, filtering, wherein filter residues are a mixture of an HZSM-5 zeolite catalyst doped with 5% (w/w) CeO2 and 2, 4-dihydroxy benzophenone, the mixture is dissolved in acetone, filtering is carried out, the filter residues are recycled to obtain the zeolite catalyst for recycling, filtrate is evaporated to obtain acetone for recycling, a crude product of the 2, 4-dihydroxy benzophenone is obtained, the crude product is recrystallized and refined by using a mixed solvent of ethanol, water and =4:1, and the crude product of the 2, 4-dihydroxy benzophenone is obtained by drying.
2. The process for synthesizing 2, 4-dihydroxybenzophenone according to claim 1, characterized in that the HZSM-5 zeolite catalyst doped with 5% (w/w) CeO2 is prepared as follows: weighing 0.5g of CeO2 and 9.5g of zeolite molecular sieve in a crucible, uniformly mixing, and baking in a muffle furnace at 500-550 ℃ to obtain the HZSM-5 zeolite catalyst doped with 5% (w/w) of CeO 2.
3. The process of claim 1, wherein the process comprises the following steps: the mass of the catalyst accounts for 1-5% of the sum of the mass of the benzoic anhydride and the mass of the resorcinol; in addition, the molar ratio of the benzoic anhydride to the resorcinol is 1 (1.6-2.0).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711061208.4A CN107879910B (en) | 2017-11-02 | 2017-11-02 | Green synthesis process of 2, 4-dihydroxy benzophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711061208.4A CN107879910B (en) | 2017-11-02 | 2017-11-02 | Green synthesis process of 2, 4-dihydroxy benzophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107879910A CN107879910A (en) | 2018-04-06 |
| CN107879910B true CN107879910B (en) | 2021-06-11 |
Family
ID=61783562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711061208.4A Active CN107879910B (en) | 2017-11-02 | 2017-11-02 | Green synthesis process of 2, 4-dihydroxy benzophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107879910B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409549B (en) * | 2018-05-10 | 2021-05-14 | 绍兴文理学院 | Preparation method of 2, 2' -dihydroxy benzophenone compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131656A (en) * | 1994-11-08 | 1996-09-25 | 通用电气公司 | Method for making acyl substituted resorcinols |
| CN101298414A (en) * | 2008-06-26 | 2008-11-05 | 华东理工大学 | Preparation of 4-hydroxy benzophenone |
| CN103709024A (en) * | 2013-12-28 | 2014-04-09 | 重庆绿色智能技术研究院 | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol |
| CN104163756A (en) * | 2014-05-21 | 2014-11-26 | 江苏德峰药业有限公司 | Synthetic method of 2-hydroxy-4-methoxybenzophenone |
-
2017
- 2017-11-02 CN CN201711061208.4A patent/CN107879910B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131656A (en) * | 1994-11-08 | 1996-09-25 | 通用电气公司 | Method for making acyl substituted resorcinols |
| CN101298414A (en) * | 2008-06-26 | 2008-11-05 | 华东理工大学 | Preparation of 4-hydroxy benzophenone |
| CN103709024A (en) * | 2013-12-28 | 2014-04-09 | 重庆绿色智能技术研究院 | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol |
| CN104163756A (en) * | 2014-05-21 | 2014-11-26 | 江苏德峰药业有限公司 | Synthetic method of 2-hydroxy-4-methoxybenzophenone |
Non-Patent Citations (4)
| Title |
|---|
| Efficient microwave-assisted direct C-benzoylation of phenols and naphthols with benzoic acid catalyzed by bismuth triflate under solvent-free or ionic liquid conditions;Tran,Phuong Hoang等;《Tetrahedron Letters (2017)》;20170307;第58卷(第16期);表1 * |
| Friedel-Crafts(傅-克)酰化反应的催化剂的研究进展;卓芸芸等;《广东化工》;20130531;第40卷(第5期);全文 * |
| Metal triflates-methanesulfonic acid as new catalytic systems: application to the Fries rearrangement;Mouhtady,Omar等;《 Tetrahedron Letters (2003)》;20030627;第44卷(第34期);全文 * |
| 沸石分子筛催化芳环化合物的Friedel Crafts酰基化反应的研究;袁冰;《中国优秀博士论文电子期刊》;20161231(第8期);第13页1.2.2.3苯酚的酰化部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107879910A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20110011917A (en) | Process for preparing of n-methyl pyrrolidone | |
| CN110452160B (en) | Preparation method of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide | |
| CN1052470C (en) | Preparation of 2,5-di-pheryl-amino-terephalsaure and it's dialkylester | |
| CN107879910B (en) | Green synthesis process of 2, 4-dihydroxy benzophenone | |
| CN106748752B (en) | A kind of preparation method of 2,3- naphthalenedicarboxylic acid | |
| CN104496820A (en) | Preparation method of light stabilizer 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate | |
| CN104803873A (en) | Method for recycling Al resources in Friedel-Crafts reaction | |
| CN109320468B (en) | Method for mild preparation of benzo [ a ] phenazine compound | |
| CN107759626B (en) | Method for preparing 4-AA by reducing inorganic reducing agent | |
| CN112604677B (en) | Catalyst, preparation method thereof and application thereof in preparation of nitroxide radical piperidinol | |
| CN111269149B (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
| CN114315575A (en) | Preparation method and application of photoinitiator intermediate | |
| CN109503343B (en) | Preparation method of photoinitiator 184 | |
| CN112457170B (en) | Preparation method of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol | |
| US9604895B2 (en) | Lactate production process | |
| CN110028379B (en) | Preparation method of 4, 4' -dichloromethyl biphenyl | |
| CN114920635B (en) | Preparation method of 4-hydroxy-1-indenone | |
| CN111138286A (en) | Method for treating mixture containing long-chain dibasic acid | |
| CN112940062B (en) | Preparation method of 16-dehydroprogesterone | |
| CN110590713B (en) | Method for synthesizing epoxyphenylethane | |
| CN114539095A (en) | Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate | |
| CN111592451B (en) | Preparation method of 4- (4-phenylbutoxy) benzoic acid | |
| CN112409420B (en) | Purification method of 2 '-fluoro-2' -deoxyuridine | |
| CN113698341B (en) | Pyridine purification method | |
| CN107032986A (en) | A kind of method that presence of acidic ionic liquid catalyst synthesizes the propanol ether acetate of 2 methoxyl group 1 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220104 Address after: 431700 No. 8 North of No. 14 Road, yuekou Industrial Park, Hubei Province Patentee after: YOUPU Biotechnology (Hubei) Co.,Ltd. Address before: 430081 Wuhan University of science and technology, 947 Heping Avenue, Qingshan District, Wuhan City, Hubei Province Patentee before: WUHAN University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right |