CN115403455A - Method for synthesizing acetophenone by oxidizing ethylbenzene - Google Patents
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 28
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- NZSLSTXKPQAVHL-UHFFFAOYSA-N 2-$l^{1}-oxidanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N([O])C(=O)C2=C1 NZSLSTXKPQAVHL-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- -1 benzyl hydrogen Chemical compound 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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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
- C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing acetophenone by oxidizing ethylbenzene, which belongs to the technical field of fine organic synthesis and can overcome the defects of harsh reaction conditions and the like existing in the acetophenone synthesis by oxidizing ethylbenzene. The method has the advantages of simple process, mild reaction conditions, high product yield and the like.
Description
Technical Field
The invention belongs to the technical field of fine organic synthesis, and particularly relates to a method for synthesizing acetophenone by oxidizing ethylbenzene.
Background
Acetophenone is an aromatic ketone widely used in industry, is also an important chemical raw material, and is widely used for synthesizing spices, dyes and medicines. Such as chloroacetophenone, mandelic acid and ibuprofen. In addition, acetophenone also generally acts as a reaction solvent, has the advantages of good stability, high boiling point and the like, and can dissolve insoluble substances such as cellulose, coumarone resin, alkyd resin and the like.
The selective oxidation of ethylbenzene to synthesize acetophenone is a research difficulty in organic synthesis, and also plays an important role in the field of petrochemical industry. In the laboratory, the acetophenone is usually prepared by using oxidizing agents such as potassium permanganate, potassium dichromate, chromium acetate/mixed anhydride and the like, but in the industry, the oxidizing agents are not used due to large use amount, serious pollution of byproducts and harsh reaction conditions. At present, the preparation of acetophenone industrially is usually completed by friedel-crafts acylation of benzene and acetyl chloride under the catalysis of aluminum trichloride, but the reaction can generate a large amount of byproduct hydrochloric acid, which causes serious corrosion to equipment and serious environmental pollution. Therefore, research and development of new green oxidation processes and oxidation systems to achieve clean production of acetophenone from ethylbenzene has become a major goal and work content of current researchers.
In recent years, a series of methods for synthesizing acetophenone have been developed, including ethylbenzene oxidation, benzoic acid decomposition, and phenethyl alcohol oxidation, among which the synthesis of acetophenone by oxidation of ethylbenzene has potential application value. A series of tetrahalogenated NHPI and DADCAQ (1,4-diamino-2,3-dichloroanthraquinone) composite catalysts were synthesized as Zhang Qiaogong et al, and after 5 h was reacted at 100 ℃ under 0.3 MPa of oxygen pressure, ethylbenzene was oxidized to synthesize acetophenone with 82.3% conversion of ethylbenzene and 86.9% selectivity of acetophenone (Journal of Chemical Technology and Biotechnology. 2008, 83: 1364-1369). Malanhong et al combine green heme with NHPI for the oxidation synthesis of acetophenone by ethylbenzene (Catalysis communications, 2007, 8: 27-30), the reaction temperature is 100 ℃, the oxygen pressure is 0.3 MPa, the reaction time is 9 h, the ethylbenzene conversion rate is 90.32%, and the selectivity is 94.3%. Wang Yifan and the like prepare a magnesium aluminum hydrotalcite (LDHs) supported MnO 4-catalyst by calcination reduction, and the catalyst is used for the oxidation of ethylbenzene, wherein the reaction temperature is 120 ℃, and the yield of acetophenone is 57% (applied chemistry, 2012, 29 (9): 1017-1022). Wang Ruixin et al, cobalt porphyrin with different structures is immobilized on high polymer modified silica gel by coordination method, and the prepared catalyst CoTNPP-P (4 VP-co-St)/SiO 2 is applied to the oxidation of ethylbenzene, 12 h is reacted at the reaction temperature of 120 ℃, and the yield of acetophenone is 25.53% (report of physical chemistry 2009, 25 (9): 1791-1798). Luo Jin et al used carbon nanotubes as catalyst, showed high stability in the reaction, oxygen pressure was 1.5 MPa, the mass ratio of catalyst to ethylbenzene was 0.2, reaction temperature was 155 ℃, reaction time was 4 h, conversion of ethylbenzene was 38.2%, and selectivity of acetophenone was 60.9% (Luo Jin. Carbon nanotubes and nitrogen-doped carbon nanotubes liquid phase catalytic oxidation of benzyl alcohol and ethylbenzene [ D ]. Guangdong: university of south China, 2013).
The preparation of acetophenone by the oxidation of ethylbenzene is one of the research hotspots, and as the alpha-H bond energy of ethylbenzene is large and activation is difficult, methods such as heavy metal catalysis or Friedel-Crafts reaction are mostly adopted in the prior art. However, these methods are generally harsh and generally require high temperature or high pressure. Therefore, the development of a new method for synthesizing acetophenone by oxidizing ethylbenzene, which has the advantages of simple process, mild reaction conditions and high reaction yield, has great practical significance and potential application value.
Disclosure of Invention
The invention provides a method for synthesizing acetophenone by oxidizing ethylbenzene, aiming at the defects of harsh reaction conditions and the like existing in the synthesis of acetophenone by oxidizing ethylbenzene.
The invention adopts the following technical scheme:
a method for synthesizing acetophenone by oxidizing ethylbenzene comprises the following steps:
firstly, adding ethylbenzene, N-hydroxyphthalimide (NHPI) and a reaction solvent into a reaction bottle in sequence;
secondly, adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.2 MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 200L/h, enabling the ozone mixed gas to enter a reaction bottle to react with reactants, and controlling the gas phase concentration of ozone to be 100-150 mg/L;
thirdly, introducing ozone mixed gas into a reaction bottle, and setting the temperature of the reaction liquid to be 25 ℃ and the reaction time to be 60 min;
and fourthly, after the reaction is finished, adding a saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by using a rotary evaporator, and then carrying out column chromatography to obtain the high-purity acetophenone.
Further, the reaction solvent in the first step includes any one of acetic acid, acetonitrile and ethyl acetate.
Further, the proportion of the ethylbenzene, the N-hydroxyphthalimide and the reaction solvent in the first step is: 5.3g:0.4 to 0.8 g:500 And (mL).
Furthermore, the eluent used for the column chromatography in the fourth step is a mixed solution of petroleum ether and dichloromethane, and the volume ratio of the eluent is 20.
The method takes ozone as an oxidant, organic micromolecular N-hydroxyphthalimide as a catalyst, under the condition of normal pressure and room temperature, N-hydroxyphthalimide (NHPI) is firstly converted into N-oxyphthalimide free radicals (PINO) through interaction, then benzyl hydrogen of ethylbenzene is captured to generate benzyloxy free radicals, the generated benzyloxy free radicals are subjected to chain growth with ozone to generate peroxy free radicals, the peroxy free radicals are decomposed into the benzyloxy free radicals and oxygen, and finally the benzyloxy free radicals generate acetophenone under the action of the PINO. The method has the advantages of simple process, mild reaction conditions, high product yield and the like.
Drawings
FIG. 1 is a formula of synthesizing acetophenone by NHPI catalyzed ozonation of ethylbenzene;
FIG. 2 is a reaction process of synthesizing acetophenone by NHPI catalyzed ozonation of ethylbenzene;
FIG. 3 shows the hydrogen spectrum of acetophenone prepared by the present invention: ( 1 H NMR)。
Detailed Description
A method for synthesizing acetophenone by oxidizing ethylbenzene comprises the following steps:
firstly, adding ethylbenzene, N-hydroxyphthalimide (NHPI) and a reaction solvent into a reaction bottle in sequence;
adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.2 MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 200L/h, enabling the ozone mixed gas to enter a reaction bottle to react with a reactant, and controlling the gas-phase concentration of ozone to be 100-150 mg/L;
thirdly, introducing ozone mixed gas into a reaction bottle, and setting the temperature of the reaction liquid to be 25 ℃ and the reaction time to be 60 min;
and fourthly, after the reaction is finished, adding a saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by using a rotary evaporator, and then carrying out column chromatography to obtain the high-purity acetophenone.
Example 1
5.3g ethylbenzene and 0.4 g NHPI were dissolved in 500 mL ethyl acetate and placed in a reaction flask, and the ozone concentration in the ozone gas phase was adjusted to 100mg/L. Reacting at 25 deg.C for 60min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether /V Methylene dichloride = 20).
1 H NMR(600 MHz, CDCl 3 ) δ 7.94-7.95 (m, 2H), 7.54 (t, J=6 Hz, 1H), 7.44 (t, J = 6 Hz, 2H), 2.58 (s, 3H)。
Example 2
5.3g ethylbenzene and 0.6 g NHPI were weighed out and dissolved in 500 mL acetic acid and placed in a reaction flask, and the ozone concentration in the ozone gas phase was adjusted to 120 mg/L. Reacting at 25 deg.C for 60min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether /V Methylene dichloride = 20).
1 H NMR(600 MHz, CDCl 3 ) δ 7.94-7.95 (m, 2H), 7.54 (t, J=6 Hz, 1H), 7.44 (t, J = 6 Hz, 2H), 2.58 (s, 3H)。
Example 3
5.3g ethylbenzene and 0.8 g NHPI were weighed out and dissolved in 500 mL acetonitrile, and placed in a reaction flask, and the ozone concentration in the ozone gas phase was adjusted to 150 mg/L. Reacting at 25 ℃ for 60mAfter in, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether /V Methylene dichloride = 20).
1 H NMR(600 MHz, CDCl 3 ) δ 7.94-7.95 (m, 2H), 7.54 (t, J=6 Hz, 1H), 7.44 (t, J = 6 Hz, 2H), 2.58 (s, 3H)。
Example 4
5.3g ethylbenzene and 0.8 g NHPI were dissolved in 500 mL ethyl acetate and placed in a reaction flask, and the ozone concentration in the ozone gas phase was adjusted to 120 mg/L. Reacting at 25 deg.C for 60min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether /V Methylene dichloride = 20).
1 H NMR(600 MHz, CDCl 3 ) δ 7.94-7.95 (m, 2H), 7.54 (t, J=6 Hz, 1H), 7.44 (t, J = 6 Hz, 2H), 2.58 (s, 3H)。
Claims (4)
1. A method for synthesizing acetophenone by oxidizing ethylbenzene is characterized by comprising the following steps: the method comprises the following steps:
firstly, adding ethylbenzene, N-hydroxyphthalimide and a reaction solvent into a reaction bottle in sequence;
secondly, adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.2 MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 200L/h, enabling the ozone mixed gas to enter a reaction bottle to react with reactants, and controlling the gas phase concentration of ozone to be 100-150 mg/L;
thirdly, introducing ozone mixed gas into a reaction bottle, and setting the temperature of the reaction liquid to be 25 ℃ and the reaction time to be 60 min;
and fourthly, after the reaction is finished, adding a saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by using a rotary evaporator, and then carrying out column chromatography to obtain the high-purity acetophenone.
2. The method for synthesizing acetophenone by oxidizing ethylbenzene according to claim 1, characterized in that: the reaction solvent in the first step includes any one of acetic acid, acetonitrile and ethyl acetate.
3. The method for synthesizing acetophenone by oxidizing ethylbenzene according to claim 1, characterized in that: in the first step, the proportion of the ethylbenzene, the N-hydroxyphthalimide and the reaction solvent is as follows: 5.3g:0.4 to 0.8 g:500 And (mL).
4. The method for synthesizing acetophenone by oxidizing ethylbenzene according to claim 1, characterized in that: and in the fourth step, the eluent used for the column chromatography is a mixed solution of petroleum ether and dichloromethane, and the volume ratio of the eluent is 20.
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| CN202211129644.1A CN115403455B (en) | 2022-09-16 | 2022-09-16 | Method for synthesizing acetophenone by oxidizing ethylbenzene |
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| CN202211129644.1A CN115403455B (en) | 2022-09-16 | 2022-09-16 | Method for synthesizing acetophenone by oxidizing ethylbenzene |
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| CN104193670A (en) * | 2014-08-11 | 2014-12-10 | 济南大学 | Synthesis and application of novel catalyst used in preparation of arone by carrying out catalytic oxidation on ethylbenzene and derivative of ethylbenzene |
| US20160159722A1 (en) * | 2013-07-18 | 2016-06-09 | Daicel Corporation | Method for producing oxide |
| US20170253575A1 (en) * | 2014-08-29 | 2017-09-07 | Daicel Corporation | Solid acid catalyst and method for producing oxide |
| CN111848371A (en) * | 2020-07-16 | 2020-10-30 | 中北大学 | Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone |
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| US20160159722A1 (en) * | 2013-07-18 | 2016-06-09 | Daicel Corporation | Method for producing oxide |
| CN104193670A (en) * | 2014-08-11 | 2014-12-10 | 济南大学 | Synthesis and application of novel catalyst used in preparation of arone by carrying out catalytic oxidation on ethylbenzene and derivative of ethylbenzene |
| US20170253575A1 (en) * | 2014-08-29 | 2017-09-07 | Daicel Corporation | Solid acid catalyst and method for producing oxide |
| CN111848371A (en) * | 2020-07-16 | 2020-10-30 | 中北大学 | Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone |
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| 张弘 等: "N-羟基邻苯二甲酰亚胺及其类似物在有机氧化反应中的研究进展", 《精细石油化工》 * |
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