CN111747833A - Method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate - Google Patents
Method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate Download PDFInfo
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- CN111747833A CN111747833A CN202010594572.2A CN202010594572A CN111747833A CN 111747833 A CN111747833 A CN 111747833A CN 202010594572 A CN202010594572 A CN 202010594572A CN 111747833 A CN111747833 A CN 111747833A
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- polyoxometallate
- phenethyl alcohol
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- acetophenone
- catalytic oxidation
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 132
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000003197 catalytic effect Effects 0.000 title claims description 37
- 230000003647 oxidation Effects 0.000 title claims description 33
- 238000007254 oxidation reaction Methods 0.000 title claims description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002390 rotary evaporation Methods 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 29
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 15
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical class OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 13
- 238000011084 recovery Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000013460 polyoxometalate Substances 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000009917 Crataegus X brevipes Nutrition 0.000 description 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 description 1
- 235000009685 Crataegus X maligna Nutrition 0.000 description 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 description 1
- 235000009486 Crataegus bullatus Nutrition 0.000 description 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 description 1
- 235000009682 Crataegus limnophila Nutrition 0.000 description 1
- 235000004423 Crataegus monogyna Nutrition 0.000 description 1
- 240000000171 Crataegus monogyna Species 0.000 description 1
- 235000002313 Crataegus paludosa Nutrition 0.000 description 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 description 1
- 229910016525 CuMo Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing acetophenone by catalyzing and oxidizing phenethyl alcohol with polyoxometallate, which comprises the following steps: taking phenethyl alcohol and a reaction solvent, taking polyoxometallate as a catalyst, mixing the phenethyl alcohol, the reaction solvent and the polyoxometallate, then carrying out reaction, and separating to obtain the acetophenone. Compared with the prior art, the method has the advantages of single raw material, simple preparation process, high product yield and no three wastes, the used catalyst is cheap and easy to obtain, and can be recycled for multiple times after simple treatment, thereby being very beneficial to industrial production, and having potential application prospect.
Description
Technical Field
The invention belongs to the field of compound preparation, and particularly relates to a method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate.
Background
Acetophenone is colorless crystal or yellowish oily liquid, has hawthorn smell, is insoluble in water, is easily soluble in most organic solvents, is insoluble in glycerol, volatilizes with steam, can generate benzoic acid during oxidation, can generate ethylbenzene during reduction, and generates ethylcyclohexane during complete hydrogenation, and is used for manufacturing toilet soap and cigarette, and also used as an intermediate for organic chemical synthesis, a solvent for fiber resin and the like and a plasticizer for plastics, and is used as a solvent for cellulose ether, cellulose ester, resin, preservative, rubber, medicine, dye and the like. The wide application leads the synthesis and application research of the acetophenone to be widely concerned by people.
The main method for preparing acetophenone at home and abroad at present specifically comprises the following steps: a250 mL four-neck flask was equipped with an electric stirrer, a thermometer, a dropping funnel and a condenser, respectively, and the upper end of the condenser was equipped with a calcium chloride drying tube connected to a hydrogen chloride gas absorption apparatus, and 39g (0.5mol) of anhydrous benzene and 40g (0.3mol) of ground anhydrous aluminum chloride were added to the four-neck flask, and 25g (0.25mol) of acetic anhydride was added dropwise under stirring. At this point the four-necked flask was cooled with cold water and acetic anhydride was added over a period of about 30 min. In order to complete the reaction, after the acetic anhydride is added dropwise, heating at 70-80 ℃ for 45min, cooling, and pouring the reactant into l00g ice water. If aluminum hydroxide precipitates, the precipitates are dissolved with concentrated hydrochloric acid, and then the benzene layer is separated. The aqueous layer was extracted with 30mL of 2 benzene, the total benzene layer solutions were combined, washed with 30mL of water, 30mL of 5 mol% sodium hydroxide solution and 30mL of water in this order, and the separated benzene layers were dried over anhydrous magnesium sulfate. And (3) distilling and recovering benzene at normal pressure, and collecting the fraction at 199-203 ℃, namely the acetophenone product. The method has the advantages of complicated steps, low yield, strict reaction conditions, strong oxidizing property of the required oxidizing agent, strong alkalinity of a reaction system, unsafe factors, high requirements on reaction equipment, and environment-friendliness of the reaction process and byproducts.
The polyoxometallate (polyacid) catalyst is a novel efficient green catalyst, not only has excellent oxidation-reduction catalytic performance, but also has high stability and high activity, and is a green and environment-friendly catalyst with a very promising prospect. Since 1927, after the reaction of catalyzing the hydration of propylene to prepare isopropanol by using polyacid as a catalyst realizes industrialization in japan, more and more researchers are put into research in the field of polyacid catalysis, wherein the more researches are mainly Dawson structures (2:18 series), Keggin structures (1:12A series), and the like. While the Anderson structure (series 1: 6) is a relatively simple polyacid, in recent years, reports on the Anderson type polyoxometallate have focused on modification of the polyacid and optimization of the structure. To date, no official literature has been reported on the application of Anderson-type polyacids to the catalytic field.
Disclosure of Invention
The invention aims to solve the problems and provide a method for preparing acetophenone by catalyzing and oxidizing phenethyl alcohol with polyoxometallate, which has the advantages of single raw material, simple preparation process, high product yield and no three wastes, and the used catalyst is cheap and easy to obtain, can be recycled for multiple times after simple treatment, is very beneficial to industrial production and has potential application prospect.
The purpose of the invention is realized by the following technical scheme:
a method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: taking phenethyl alcohol and a reaction solvent, taking polyoxometallate as a catalyst, mixing the phenethyl alcohol, the reaction solvent and the polyoxometallate, reacting, washing by an organic solvent and carrying out rotary evaporation to obtain the acetophenone. The reaction is carried out in a clean reaction vessel, and an oxygen balloon is sleeved on the upper part of the reactor before the reaction (the catalytic efficiency is higher in a pure oxygen atmosphere), and the equation of the reaction is shown as the following formula (I):
preferably, the reaction solvent is acetonitrile and the organic solvent is ethyl acetate.
Preferably, the polyoxometallate is selected from one or more of a Keggin-type, Wells-Dawson-type, Anderson-type, Lindqvist-type, Waugh-type or Silverton-type configuration.
Preferably, the polyoxometallate is in an Anderson-type configuration.
Preferably, the polyoxometallate is a non-noble metal-centered polyoxometallate.
Preferably, the non-noble metal is selected from one or more of Fe, Cu, Ni or Cr.
Preferably, the polyoxometalate is a trialkoxy derivative (Tris derivative) modified non-noble metal-centered Anderson-type polyoxometalate.
Preferably, the non-noble metal is selected from one or more of Fe, Cu, Ni or Cr.
Preferably, the molar amount of the polyoxometallate is 0.1-5%, preferably 1%, of the molar amount of the phenethyl alcohol.
Preferably, the reaction temperature is 0-100 ℃, and the reaction time is 5-24 h. Further preferably, the reaction temperature is 80 ℃ and the reaction time is 10 h.
Preferably, magnetic stirring is carried out while the reaction is carried out, the stirring time is 5-24 h, and the stirring speed is 1000-2000 rpm. Further preferably, the stirring time is 10h and the stirring rate is 1200 rpm.
Preferably, the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 h.
Preferably, the polyoxometallate after the recovery reaction of the organic solvent is used as the catalyst for recycling.
Preferably, the organic solvent is selected from one or more of diethyl ether, ethanol or methanol. The recovered catalyst is recycled, the recovered polyacid is reused for preparing acetophenone by catalytic oxidation of phenethyl alcohol, and the catalytic activity of the polyoxometallate is investigated.
The method takes polyoxometallate (wherein the polyoxometallate is one of six basic configurations of Keggin type, Wells-Dawson type, Anderson type, Lindqvist type, Waugh type and Silverton type, and the Anderson type configuration is taken as a main configuration) as a catalyst, and takes acetonitrile as a reaction solvent to catalyze phenethyl alcohol to react to obtain the acetophenone. According to the method, the acetophenone is prepared by catalyzing and oxidizing phenethyl alcohol by adopting the heteropolyacid taking non-noble metals such as Fe, Cu, Ni and Cr as central metals as the catalyst, the catalyst has extremely high reaction activity, the used catalyst can be recycled after the sample is simply treated after the reaction is finished, the method is environment-friendly, the cleanness of the reaction is improved, the production and manufacturing cost is reduced, and the method is easy to control and industrially produce.
Compared with the prior method for preparing acetophenone, the method has the following advantages: the method has the advantages of single raw material, low price, simple preparation process, high product yield, no three wastes, environmental friendliness and the like, the used catalyst is a novel catalyst, namely Anderson type polyoxometallate (heteropoly acid), the central metals are common non-noble metals Fe, Cu, Ni and Cr, the price is low, the catalyst is easy to obtain, and the catalyst can be recycled for multiple times after simple treatment, so the method is very favorable for industrial production, and has potential application prospect.
Drawings
FIG. 1 is a reaction equation for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate;
fig. 2 is a schematic structural diagram of six crystal configurations, from left to right: lindqvist, Keggin, Wells-Dawson, Anderson, Waugh, and Silverton configurations;
FIG. 3 is a topological diagram of the structure of Anderson type heteropolyacids;
FIG. 4 is a topological diagram of a Tris ligand modified Anderson type heteropolyacid structure;
FIG. 5 shows an Anderson-based polyoxometallate IR spectrum and a Tris derivative-modified Anderson-based polyoxometallate IR spectrum (taking copper as the metal center as an example);
FIG. 6 is a comparison of XRD of polyoxometallate based on Anderson and its multiple recycles (taking copper as the metal center as an example);
FIG. 7 shows the nuclear magnetic spectrum of an Anderson polyoxometallate modified with Tris derivatives (taking copper as the metal center as an example);
FIG. 8 is an SEM image of Anderson-type polyoxometallate at different magnifications (taking copper as the metal center for example);
FIG. 9 is an SEM image of Tris derivative modified Anderson polyoxometallates at different magnifications (taking copper as the metal center for example);
FIG. 10 shows the preparation of acetophenone by catalytic oxidation of phenethyl alcohol with Anderson-type polyoxometallate (taking copper as metal center as example)1HNMR map.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: taking phenylethanol and a reaction solvent, taking polyoxometallate as a catalyst, mixing the phenylethanol, the reaction solvent and the polyoxometallate, then carrying out a reaction, separating to obtain acetophenone, and adding an organic solvent into a system after the reaction to precipitate the polyoxometallate, wherein the equation of the reaction is specifically shown in figure 1. Wherein the polyoxometallate is selected from one or more of Keggin type, Wells-Dawson type, Anderson type, Lindqvist type, Waugh type or Silverton type configurations, specifically as shown in FIG. 2, FIG. 3 is a topological diagram of the Anderson type heteropolyacid structure, FIG. 4 is a topological diagram of the Tris ligand modified Anderson type heteropolyacid structure, FIG. 5 is an infrared spectrum (CuMo 6) of the Anderson type polyoxometallate and an infrared spectrum (NH 2-CuMo6) of the Tris derivative modified Anderson type polyoxometallate (taking copper as a metal center as an example), FIG. 6 is a comparison graph of XRD of the Anderson type polyoxometallate and XRD after multiple recycling (taking copper as a metal center as an example), FIG. 7 is an NMR spectrum (taking copper as an example) of the Tris derivative modified Anderson type polyoxometallate and FIG. 8 is an enlarged diagram of the copper element SEM (taking copper center as an example), FIG. 9 is an SEM image of Tris derivative modified Anderson polyoxometallates at different magnifications (taking copper as the metal center for example).
Example 1
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: a25 mL clean reaction tube was charged with 0.0242g (0.02mmol) of a nickel-centered polyoxometalate [ NH ]4]4[NiMo6O18(OH)6]·7H2O(NiMo6) (purchased directly from Beijing, Hongyaosen Biotechnology Co., Ltd., cat-474, cat-cat), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally, a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by using a magnetic stirrer; after the reaction is finished, sampling and measuring GCMS, knowing that the conversion rate of a reaction substrate is more than 93 percent and the selectivity of a product is 92 percent, washing the reaction substrate by ethyl acetate and carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is long)6h), then separating and purifying, and then confirming the product acetophenone by GCMS.
Example 2
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: a25 mL clean reaction tube was charged with 0.0244g (0.02mmol) of iron-centered polyoxometallate [ NH ]4]3[FeMo6O18(OH)6]·7H2O(FeMo6) (purchased directly from Beijing, Haoyason Biotechnology Ltd., cat-472), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 92 percent, the selectivity of the product is 95 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 hours), separating and purifying, and then carrying out magnetic confirmation by GCMS to obtain the product acetophenone.
Example 3
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: 0.0241g (0.02mmol) of copper-centered polyoxometallate [ NH ] was charged into a 25mL clean reaction tube4]4[CuMo6O18(OH)6]·7H2O(CuMo6) (purchased directly from Beijing, Hongshiansen Biotechnology Co., Ltd., cat-475), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally, a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by using a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, obtaining that the conversion rate of a reaction substrate is more than 93%, the selectivity of a product is 91%, washing with ethyl acetate, performing rotary evaporation (the rotary evaporation temperature is 100 ℃ and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is acetophenone by GCMS, wherein as shown in figure 10, the peak position shown in the figure is an acetophenone standard peak value, and the product is confirmed to be acetophenone by matching of a GCMS standard substance map library.
Example 4
A method for preparing acetophenone by catalyzing and oxidizing phenethyl alcohol with polyoxometallate,the method specifically comprises the following steps: a25 mL clean reaction tube was charged with 0.0242g (0.02mmol) of chromium-centered polyoxometallate [ NH ]4]3[CrMo6O18(OH)6]·7H2O(CrMo6) (purchased directly from Beijing, Hongshiansen Biotech Co., Ltd., cat-480), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 94 percent and the selectivity of the product is 91 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃ and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is the acetophenone by GCMS.
Example 5
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: 0.0402g (0.02mmol) of a Tris derivative single-side modified nickel-centered polyoxometalate [ N (C) ]was put into a 25mL clean reaction tube4H9)4]4[NiMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-NiMo6) (purchased directly from Beijing, Hongshiansen Biotech Co., Ltd., cat-B474), 10mL of acetonitrile and 2mmol of phenethyl alcohol, and finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube to react for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by using a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 92 percent, the selectivity of the product is 91 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is the acetophenone by GCMS.
Example 6
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: 0.0405g (0.02mmol) of an iron-centered polyoxometalate which is modified on one side with a Tris derivative [ [ N (C) was put into a 25mL clean reaction tube4H9)4]3[FeMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-FeMo6) (purchased directly from Beijing, Haoyason Biotechnology Ltd., cat-B472), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 93 percent, the selectivity of the product is 92 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is the acetophenone by GCMS.
Example 7
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: 0.0404g (0.02mmol) of copper-centered polyoxometallate modified on one side with a Tris derivative [ [ N (C) ] was added to a 25mL clean reaction tube4H9)4]4[CuMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CuMo6) (purchased directly from Beijing Haoyason Biotechnology Ltd., cat-B475, cat-B), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally covering a balloon filled with oxygen above the reaction tube, reacting for 10h at 80 ℃, and magnetically stirring for 10h at 1200rpm by using a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 90 percent, the selectivity of the product is 91 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is the acetophenone by GCMS.
Example 8
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate comprises the following steps: 0.0407g (0.02mmol) of chromium-centered polyoxometallate modified on one side with a Tris derivative [ [ N (C) ] was added to a 25mL clean reaction tube4H9)4]3[CrMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CrMo6) (purchased directly from Beijing, Hongshiansen Biotech Co., Ltd., cat-B480), 10mL acetonitrile, 2mmol phenethyl alcohol, and finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube, the reaction is carried out for 10h at 80 ℃, and magnetic stirring is carried out for 10h at the speed of 1200rpm by a magnetic stirrer; after the reaction is finished, sampling and detecting GCMS, knowing that the conversion rate of a reaction substrate is more than 92 percent, the selectivity of the product is 90 percent, washing by ethyl acetate, carrying out rotary evaporation (the rotary evaporation temperature is 100 ℃, and the rotary evaporation time is 6 hours), separating and purifying, and then confirming that the product is the acetophenone by GCMS.
Example 9
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate is the same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 1 st time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is more than 92 percent, the selectivity is about 91 percent, and a product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
Example 10
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate is the same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 2 nd time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is more than 91 percent, the selectivity is about 89 percent, and a product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
Example 11
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate is the same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 3 rd time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is 89%, the selectivity is about 88%, and a product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
Example 12
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate comprises the following reaction steps of the same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 4 th time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is 87 percent, the selectivity is about 86 percent, and a product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
Example 13
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate is the same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 5 th time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is 85 percent, the selectivity is about 82 percent, and a product is obtained by separation and purification, and GCMS confirms acetophenone.
Example 14
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate, except that the used catalyst is recovered by diethyl ether and is used for the 6 th time after recovery, the rest reaction steps are the same as those in the example 7, GCMS analysis shows that the conversion rate of a reaction substrate is 81 percent, the selectivity is about 80 percent, and a product is obtained by separation and purification, GCMS confirms acetophenone, the XRD of polyoxometallate after the 6 th time of recovery and utilization is compared with the XRD of new polyoxometallate, as shown in figure 6, it can be seen that the polyoxometallate is basically unchanged after multiple recovery, the peak position shows the component composition of the catalyst, the peak value shows the content of the catalyst, and as shown in figure 6, the catalyst composition is almost unchanged, namely, after multiple times of reaction and recovery, the structure of the catalyst is approximately stable and can be recycled.
Example 15
A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate comprises the following reaction steps of same as example 7 except that the used catalyst is recovered by diethyl ether and is used for the 7 th time after recovery, GCMS analysis shows that the conversion rate of a reaction substrate is 79 percent, the selectivity is about 78 percent, and a product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
Example 7 and examples 9-15 show that the polyoxometalate catalyst has good catalytic performance after multiple recoveries.
Example 16
Except that the molar amount of the polyoxometallate is 0.1 percent of the molar amount of the phenethyl alcohol, the reaction temperature is 0 ℃, the reaction time is 24 hours, the stirring speed is 2000rpm, the ethanol is adopted for recovering the catalyst, the rest is the same as the example 7, the conversion rate of a reaction substrate is more than 92 percent, the selectivity is about 91 percent, the product is obtained by separation and purification, and GCMS confirms that the acetophenone is used.
Example 17
The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate is the same as that in example 7 except that the molar amount of the polyoxometallate is 5 percent of that of the phenethyl alcohol, the reaction temperature is 100 ℃, the reaction time is 5 hours, the stirring speed is 1000rpm, the catalyst is recovered by adopting methanol, the conversion rate of a reaction substrate is more than 92 percent, the selectivity is about 91 percent, the product is obtained by separation and purification, and GCMS confirms that the acetophenone is obtained.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for preparing acetophenone by catalytic oxidation of phenethyl alcohol by polyoxometallate is characterized by comprising the following steps: taking phenethyl alcohol and a reaction solvent, taking polyoxometallate as a catalyst, mixing the phenethyl alcohol, the reaction solvent and the polyoxometallate, reacting, washing by an organic solvent and carrying out rotary evaporation to obtain the acetophenone.
2. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the reaction solvent is acetonitrile and the organic solvent is ethyl acetate.
3. The method for preparing acetophenone by the catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the polyoxometallate is selected from one or more of Keggin type, Wells-Dawson type, Anderson type, Lindqvist type, Waugh type or Silverton type configurations.
4. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the polyoxometallate is non-noble metal-centered polyoxometallate.
5. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the polyoxometallate is trialkoxy derivative modified non-noble metal-centered Anderson type polyoxometallate.
6. The method for preparing acetophenone by oxidizing phenethyl alcohol with polyoxometallate as shown in claim 4 or 5, characterized in that the non-noble metal is selected from one or more of Fe, Cu, Ni or Cr.
7. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the molar amount of the polyoxometallate is 0.1-5% of the molar amount of the phenethyl alcohol.
8. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that the reaction temperature is 0-100 ℃ and the reaction time is 5-24 h.
9. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that magnetic stirring is carried out while the reaction is carried out, the stirring time is 5-24 h, and the stirring speed is 1000-2000 rpm.
10. The method for preparing acetophenone by catalytic oxidation of phenethyl alcohol with polyoxometallate according to claim 1, characterized in that organic solvent is used to recover the polyoxometallate after reaction.
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CN115677462A (en) * | 2021-07-29 | 2023-02-03 | 安徽圣诺贝化学科技有限公司 | Method for preparing citronellal by catalytic oxidation of citronellol |
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---|
SHAN-SHUI MENG ETAL: ""Aerbic oxidation of alcohols with air catalyzed by decacarbonyldimanganese"", 《GREEN CHEMISTRY》 * |
ZHEYU WEI ETAL: ""Highly efficient and practical aerobic oxidation of alcohols by inorganic-ligand supported copper catalysis"", 《GREEN CHEMISTRY》 * |
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CN115677462A (en) * | 2021-07-29 | 2023-02-03 | 安徽圣诺贝化学科技有限公司 | Method for preparing citronellal by catalytic oxidation of citronellol |
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