CN111978170A - Green recyclable synthesis method of phenylacetic acid - Google Patents
Green recyclable synthesis method of phenylacetic acid Download PDFInfo
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- CN111978170A CN111978170A CN201910439872.0A CN201910439872A CN111978170A CN 111978170 A CN111978170 A CN 111978170A CN 201910439872 A CN201910439872 A CN 201910439872A CN 111978170 A CN111978170 A CN 111978170A
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- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229960003424 phenylacetic acid Drugs 0.000 title claims abstract description 38
- 239000003279 phenylacetic acid Substances 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 230000005496 eutectics Effects 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 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 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002360 explosive Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- DRHTUSJYFUOTSH-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;propane-1,2,3-triol;chloride Chemical compound [Cl-].OCC(O)CO.C[N+](C)(C)CCO DRHTUSJYFUOTSH-UHFFFAOYSA-M 0.000 description 1
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 102000018997 Growth Hormone Human genes 0.000 description 1
- 108010051696 Growth Hormone Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- AEDFCLSZQKLJJA-UHFFFAOYSA-M ethane-1,2-diol;2-hydroxyethyl(trimethyl)azanium;chloride Chemical compound [Cl-].OCCO.C[N+](C)(C)CCO AEDFCLSZQKLJJA-UHFFFAOYSA-M 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000122 growth hormone Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of organic synthesis, and provides a green recyclable synthetic method of phenylacetic acid, which comprises the following steps: reacting toluene and carbon monoxide in the presence of a catalyst and a solvent to obtain phenylacetic acid; the catalyst comprises an active component and a carrier, wherein the active component comprises one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr; the solvent is an ionic liquid and/or a eutectic solvent; the reaction temperature is 60-90 ℃, and the reaction pressure is normal pressure. The catalyst can be recycled and regenerated, so that the production cost is effectively reduced, and the waste of resources is avoided; the yield of the phenylacetic acid obtained by the method provided by the invention is high and can reach more than 75%, and the yield of the phenylacetic acid can still be kept more than 50% after the catalyst is recycled for 5 times. In addition, the method provided by the invention has mild conditions and does not need flammable and explosive alkali metal sodium.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a green recyclable synthesis method of phenylacetic acid.
Background
Phenylacetic acid is an important organic synthesis intermediate, is commonly used for the production of medicines, pesticides, spices and the like, and is also a pesticide plant growth hormone, and has strong bactericidal action, so that the phenylacetic acid has wide application in production and life.
The current methods for synthesizing phenylacetic acid include various methods such as a sodium cyanide method, a styrene method, acetophenone, and the like. In the method, the sodium cyanide method is widely applied, but the sodium cyanide method needs to use metallic sodium in the reaction process, and the metallic sodium is active, flammable and explosive and has certain danger; and after the reaction, the metal sodium can not be recycled, which causes resource waste.
Disclosure of Invention
The invention provides a green recyclable synthesis method of phenylacetic acid, which has mild reaction conditions and does not need flammable and explosive alkali metal sodium; in addition, in the synthesis method provided by the invention, the catalyst can be recycled, the production cost is effectively reduced, and the waste of resources is avoided.
The invention provides a green recyclable synthesis method of phenylacetic acid, which comprises the following steps: reacting toluene and carbon monoxide in the presence of a catalyst and a solvent to obtain phenylacetic acid;
The catalyst comprises an active component and a carrier, wherein the active component comprises one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr;
the solvent is an ionic liquid and/or a eutectic solvent;
the reaction temperature is 60-90 ℃, and the reaction pressure is normal pressure.
Preferably, the pH value of the reaction is 7-10.
Preferably, the active component in the catalyst is loaded on a carrier, and the content of the active component in the catalyst is 0.5-10 wt%.
Preferably, the carrier in the catalyst comprises one or more of molecular sieve, mesoporous carbon and polymer microspheres.
Preferably, the catalyst also comprises an auxiliary agent, and the content of the auxiliary agent in the catalyst is 0.5-5 wt%.
Preferably, the ionic liquid comprises one or more of ammonium salts, pyridines and imidazoles; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is quaternary ammonium salt, and the hydrogen bond donor is urea, carboxylic acid, polyalcohol or amino acid.
Preferably, the molar ratio of the toluene to the carbon monoxide is 1: 1.2-2.
Preferably, the molar ratio of the active component to the toluene in the catalyst is 0.001-0.005: 1.
Preferably, after the reaction is completed, the method further comprises: filtering the reaction solution to obtain a filter cake and a filtrate; washing the filter cake with water, and recovering to obtain a catalyst; the filtrate is sequentially acidified, extracted and evaporated to obtain the phenylacetic acid.
Preferably, the method for regenerating the recovered catalyst comprises the following steps: soaking the recovered catalyst in 0.001-0.1 mol/L metal precursor solution for 12-14 h; the metal precursor solution includes a metal nitrate solution or a metal chloride solution.
The invention provides a green recyclable synthesis method of phenylacetic acid, which comprises the following steps: reacting toluene and carbon monoxide in the presence of a catalyst and a solvent to obtain phenylacetic acid; the catalyst comprises an active component and a carrier, wherein the active component comprises one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr; the solvent is an ionic liquid and/or a eutectic solvent; the reaction temperature is 60-90 ℃, and the reaction pressure is normal pressure.
The catalyst in the synthesis method provided by the invention can be recycled, and the catalyst can be regenerated, so that the production cost is effectively reduced, and the waste of resources is avoided; the yield of the phenylacetic acid obtained by the method provided by the invention is high and can reach more than 75%, and the yield of the phenylacetic acid can still be kept more than 50% after the catalyst is recycled for 5 times. In addition, the method provided by the invention has mild conditions and does not need flammable and explosive alkali metal sodium.
Drawings
FIG. 1 is a GC-MS spectrum of phenylacetic acid prepared in example 1 of the present invention;
FIG. 2 is a mass spectrum of phenylacetic acid prepared in example 1 of the present invention.
Detailed Description
The invention provides a green recyclable synthesis method of phenylacetic acid, which comprises the following steps: reacting toluene and carbon monoxide in the presence of a catalyst and a solvent to obtain phenylacetic acid;
the catalyst comprises an active component and a carrier, wherein the active component comprises one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr;
the solvent is an ionic liquid and/or a eutectic solvent;
the reaction temperature is 60-90 ℃, and the reaction pressure is normal pressure.
The invention makes toluene and carbon monoxide react in the presence of catalyst and solvent to obtain phenylacetic acid.
In the present invention, the catalyst comprises an active component and a carrier, the active component comprising one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr; the carrier preferably comprises one or more of a molecular sieve, mesoporous carbon and polymeric microspheres, the molecular sieve further preferably comprising MCM-41 or SBA-15. In the invention, the active component is loaded on a carrier, and the content of the active component in the catalyst is preferably 0.5-10 wt%, more preferably 1-8 wt%, and even more preferably 2-6 wt%.
The catalyst provided by the invention preferably comprises an auxiliary agent, and the auxiliary agent preferably comprises one or more of Na, K, Al, Mn and V. In the invention, the content of the auxiliary agent is preferably 0.5 to 5 wt%, more preferably 1 to 4 wt%, and even more preferably 2 to 3 wt%. The preparation method of the catalyst is not particularly required, and the immobilization of the active component and the auxiliary agent can be realized by adopting an impregnation method, an ion exchange method or a hydrothermal method which are well known by the technical personnel in the field. The catalyst provided by the invention preferably contains an auxiliary agent, which is beneficial to further improving the yield of phenylacetic acid.
In the present invention, the solvent is an ionic liquid and/or a eutectic solvent, and the ionic liquid preferably includes one or more of ammonium salts, pyridines and imidazoles, and further preferably includes [ bmin [ ]]PF6、[C6min]Cl、[C4min]BF4、[bmin]Br-FeCl3And [ omim][BF4]One or more of; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is preferably quaternary ammonium salt, and the hydrogen bond donor is preferably urea, carboxylic acid, polyalcohol or amino acid; the eutectic solvent further preferably includes one or more of urea-choline chloride, ethylene glycol-choline chloride, and glycerol-choline chloride. In the present invention, the mass ratio of the solvent to toluene is preferably 3 to 10:1, and more preferably 5 to 8: 1.
In the invention, toluene and carbon monoxide react in the presence of a catalyst and a solvent to obtain benzoic acid, wherein the reaction formula is shown as formula I:
in the present invention, the molar ratio of toluene to carbon monoxide is preferably 1:1.2 to 2, and more preferably 1:1.5 to 1.8.
In the present invention, the molar ratio of the active ingredient to toluene in the catalyst is preferably 0.001 to 0.005:1, and more preferably 0.001: 1.
In the invention, the reaction temperature is 60-90 ℃, and preferably 70-80 ℃; the reaction time is preferably 2-6 h, and more preferably 3-4 h; the reaction is carried out under normal pressure conditions.
In the invention, the pH value of the reaction is preferably 7-10, more preferably 8-9, the pH value of the reaction is preferably adjusted by adding triethylamine and water, and the invention has no special requirement on the dosage of triethylamine and water as long as the requirement on the pH value of the reaction system can be met.
After the reaction of toluene and carbon monoxide is completed, the reaction solution is preferably filtered to obtain a filter cake and a filtrate; washing the filter cake with water, and recovering to obtain a catalyst; the filtrate is sequentially acidified, extracted and evaporated to obtain the phenylacetic acid. The invention does not require any particular embodiment of the water washing of the filter cake, and methods known to those skilled in the art can be used.
In the present invention, the method for regenerating the recovered catalyst preferably comprises the steps of: soaking the recovered catalyst in 0.001-0.1 mol/L metal precursor solution for 12-14 h; the metal precursor solution preferably comprises a metal nitrate solution or a metal chloride solution.
In the invention, the main component of the filtrate is phenylacetate, the filtrate is preferably acidified by hydrochloric acid to convert the phenylacetate into phenylacetic acid, after the acidification is finished, the acidified filtrate is preferably extracted by diethyl ether, and then the extract (organic phase) is evaporated to remove the diethyl ether, so that the phenylacetic acid is obtained. The present invention is not particularly limited to the specific embodiments of the extraction and evaporation processes, and may be practiced in a manner well known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Soaking 2g of MCM-41 in 8mL of palladium chloride aqueous solution (the concentration is 0.023mol/L) for 4h, drying at 80 ℃ overnight, and roasting at 550 ℃ for 4h to obtain a 1 wt% Pd/MCM-41 catalyst;
2000g of bmin is added into a reaction kettle]PF649.8g of a 1 wt% Pd/MCM-41 catalyst. After stirring, 404.8g of toluene (4.4mol), 890.5g of triethylamine (8.8mol) and 396g of water were added. Introducing CO at normal temperature to keep the kettle pressure at 1 MPa. Heating to 70 ℃ for reaction for 3h, and cooling to room temperature. And replacing the reaction solution with nitrogen for three times, carrying out suction filtration on the reaction solution to obtain a filter cake and filtrate, washing the filter cake with water for three times, recovering the catalyst, acidifying the filtrate with hydrochloric acid, extracting with diethyl ether, and then evaporating the diethyl ether to obtain phenylacetic acid, wherein the yield of the phenylacetic acid is 85 percent, and the purity of the phenylacetic acid is 99 percent. The recovered catalyst was treated with 0.023mol/L of PdCl 2The solution is soaked for 12 hours at room temperature, and is used for the second reaction after being dried, and the reaction yield is highReaching 80 percent; after the reaction solution is repeatedly used for five times, the reaction yield can still reach 57%.
The phenylacetic acid prepared in example 1 was subjected to GC-MS test, the test results are shown in fig. 1, and the phenylacetic acid prepared in example 1 was subjected to mass spectrometry test, the test results are shown in fig. 2. As can be seen from FIGS. 1 and 2, the product produced in example 1 of the present invention was phenylacetic acid.
Example 2
The preparation method of the Fe-Cu/SBA-15 catalyst comprises the following steps: 18mL of an aqueous iron nitrate solution (concentration: 0.02mol/L) and 16mL of an aqueous copper nitrate solution (concentration: 0.02mol/L) were mixed to obtain a mixed solution, 2g of SBA-15 was immersed in the mixed solution for 4 hours, dried overnight at 80 ℃ and calcined at 550 ℃ for 4 hours to obtain 1 wt% Fe-1 wt% Cu/SBA-15 catalyst.
2000g of C is added into a reaction kettle6min]Cl, 49.8g of 1 wt% Fe-1 wt% Cu/SBA-15 catalyst. After stirring, 404.8g of toluene (4.4mol), 890.5g of triethylamine (8.8mol) and 396g of water were added. Introducing CO at normal temperature to keep the kettle pressure at 1 MPa. Heating to 80 ℃ for reaction for 2h, and cooling to room temperature. And (2) after replacing the reaction solution with nitrogen for four times, carrying out suction filtration on the reaction solution to obtain a filter cake and a filtrate, washing the filter cake with water for three times, recovering the catalyst, acidifying the filtrate with hydrochloric acid, extracting with diethyl ether, and then evaporating the diethyl ether to obtain phenylacetic acid, wherein the yield of the phenylacetic acid is 85%, and the purity of the phenylacetic acid is 98%. The recovered catalyst is used with 0.02mol/L of FeNO 3And 0.02mol/L of CuNO3The solution is soaked for 12 hours at room temperature, and is used for the second reaction after being dried, and the reaction yield reaches 80 percent; after the reaction is repeatedly used for five times, the reaction yield can still reach 60 percent.
Example 3
The preparation method of the Ag/SBA-15 catalyst comprises the following steps: soaking 2g of SBA-15 in 10mL of silver nitrate aqueous solution (the concentration is 0.02mol/L) for 4h, drying at 80 ℃ overnight, and roasting at 550 ℃ for 4h to obtain the 1 wt% Ag/SBA-15 catalyst.
2000g of omim is added into a reaction kettle][BF4]49.8g of a 1 wt% Ag/SBA-15 catalyst. After stirring, 404.8g of toluene (4.4mol), 890.5g of triethylamine (8.8mol) and 396g of water were added. Introducing CO at normal temperature to keep the kettle pressure at 1 MPa. Heating to 80 ℃ for reaction for 2h, and cooling to room temperature. Replacing the reaction solution with nitrogen five times, and then adding the mixtureAnd (3) carrying out suction filtration to obtain a filter cake and a filtrate, washing the filter cake for three times with water, recovering to obtain a catalyst, acidifying the filtrate with hydrochloric acid, extracting with diethyl ether, and then evaporating the diethyl ether to obtain phenylacetic acid, wherein the yield of the phenylacetic acid is 77%, and the purity of the phenylacetic acid is 98.5%. The recovered catalyst is used with 0.02mol/L AgNO3The solution is soaked for 12 hours at room temperature, and is used for the second reaction after being dried, and the reaction yield reaches 71 percent; after the reaction solution is repeatedly used for five times, the reaction yield can still reach 51 percent.
The results of GC-MS test and mass spectrometry test on phenylacetic acid prepared in examples 2 and 3 were similar to those of example 1, and thus it was demonstrated that phenylacetic acid was the product prepared in examples 2 to 3.
In conclusion, the phenylacetic acid obtained by the method provided by the invention has high yield which can reach more than 75%, and the yield which can reach more than 80% by adopting the bimetallic catalyst. In the method provided by the invention, the catalyst can be recycled, the yield of the phenylacetic acid can still be kept above 50% after the catalyst is recycled for 5 times, and the yield of the phenylacetic acid can be kept above 55% after the catalyst is recycled for 5 times when the bimetallic catalyst is adopted, so that the production cost is effectively reduced, and the waste of resources is avoided. In addition, the method provided by the invention has mild conditions and does not need flammable and explosive alkali metal sodium.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A green recyclable synthesis method of phenylacetic acid comprises the following steps: reacting toluene and carbon monoxide in the presence of a catalyst and a solvent to obtain phenylacetic acid;
the catalyst comprises an active component and a carrier, wherein the active component comprises one or more of Pd, Pt, Au, Ag, Co, Cu, Ni, Fe and Cr;
The solvent is an ionic liquid and/or a eutectic solvent;
the reaction temperature is 60-90 ℃, and the reaction pressure is normal pressure.
2. The synthesis method according to claim 1, wherein the reaction has a pH of 7 to 10.
3. The synthesis method according to claim 1, wherein the active component in the catalyst is supported on a carrier, and the content of the active component in the catalyst is 0.5-10 wt%.
4. A synthesis method according to claim 1 or 3, characterised in that the support in the catalyst comprises one or more of molecular sieves, mesoporous carbon and polymeric microspheres.
5. The synthesis method according to claim 1, wherein the catalyst further comprises an auxiliary agent, and the content of the auxiliary agent in the catalyst is 0.5-5 wt%.
6. The method of claim 1, wherein the ionic liquid comprises one or more of ammonium salts, pyridines, and imidazoles; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is quaternary ammonium salt, and the hydrogen bond donor is urea, carboxylic acid, polyalcohol or amino acid.
7. The synthesis method according to claim 1, wherein the molar ratio of toluene to carbon monoxide is 1: 1.2-2.
8. The synthesis method according to claim 1, wherein the molar ratio of the active component to toluene in the catalyst is 0.001-0.005: 1.
9. The method of synthesis according to claim 1, further comprising, after completion of the reaction: filtering the reaction solution to obtain a filter cake and a filtrate; washing the filter cake with water, and recovering to obtain a catalyst; the filtrate is sequentially acidified, extracted and evaporated to obtain the phenylacetic acid.
10. The synthesis process according to claim 9, characterized in that the method of regenerating the recovered catalyst comprises the following steps: soaking the recovered catalyst in 0.001-0.1 mol/L metal precursor solution for 12-14 h; the metal precursor solution includes a metal nitrate solution or a metal chloride solution.
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| CN114835542A (en) * | 2021-02-02 | 2022-08-02 | 中国科学技术大学 | Method for synthesizing aryl acetic acid by directly carbonylating alkyl aromatic hydrocarbon and water |
| CN114956983A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Production method of phenylacetic acid |
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