CN105121399B - The synthetic method of 1-Phenylethanone. - Google Patents
The synthetic method of 1-Phenylethanone. Download PDFInfo
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- CN105121399B CN105121399B CN201480022480.XA CN201480022480A CN105121399B CN 105121399 B CN105121399 B CN 105121399B CN 201480022480 A CN201480022480 A CN 201480022480A CN 105121399 B CN105121399 B CN 105121399B
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- Prior art keywords
- phenylethanone
- oxidation reaction
- ethylo benzene
- compound
- cobalt
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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 150
- 238000010189 synthetic method Methods 0.000 title description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 192
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims description 73
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000003960 organic solvent Substances 0.000 claims description 27
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000003513 alkali Substances 0.000 description 25
- 235000013495 cobalt Nutrition 0.000 description 22
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 150000007524 organic acids Chemical class 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- -1 imide compound Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical class CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- BUXKULRFRATXSI-UHFFFAOYSA-N 1-hydroxypyrrole-2,5-dione Chemical class ON1C(=O)C=CC1=O BUXKULRFRATXSI-UHFFFAOYSA-N 0.000 description 1
- UFAKGZMZIPCHEA-UHFFFAOYSA-N 2-hydroxy-4-nitroisoindole-1,3-dione Chemical class C1=CC([N+]([O-])=O)=C2C(=O)N(O)C(=O)C2=C1 UFAKGZMZIPCHEA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical class ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000010855 food raising agent Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
-
- 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))
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to pass through the method that selective oxidation ethylo benzene synthesizes 1-Phenylethanone..According to the present invention, there is provided the method that simplified technique synthesizes 1-Phenylethanone. with higher yields high-volume can be passed through.
Description
Technical field
The present invention relates to be used to prepare the method for 1-Phenylethanone., and more particularly, to for by selective oxidation second
The method that base benzene prepares 1-Phenylethanone..
Background technology
1-Phenylethanone. is aromatic ketone, its be for prepare various kinds of resin, medicine, spice and the like it is useful before
Body.
1-Phenylethanone. can be obtained by various methods.For example, which can pass through the Fu Ke (Friedel- of benzene and acetic anhydride
Craft) react to synthesize.However, the synthetic method has significant environmental drawbacks, because producing after the reaction was completed a large amount of
Acid waste water and production in enormous quantities be difficult.
Additionally, when phenol is prepared by isopropyl benzene process, 1-Phenylethanone. can be obtained as by-product.However, according to
The method, the amount of the 1-Phenylethanone. that can be prepared are determined according to the supply and demand of the preparation condition or phenol of isopropyl benzene process.
Recently, it has been suggested that pass through 1- phenylethanols, ethylo benzene, toluene and class in the presence of the catalyst comprising palladium
Like the method that the oxidation reaction of thing synthesizes 1-Phenylethanone..The subject matter of the synthetic method includes the technique of complexity and the reaction for extending
Time.In the oxidation reaction, 1-Phenylethanone. is to be oxidized to benzoic intermediate, and under oxidative conditions, reaction is easily entered
Row is to benzoic acid.
So, the in itself previously known synthetic method of 1-Phenylethanone. is related to relative complex technique, needs expensive raw material chemical combination
Thing, and there is on the yield for guaranteeing synthetic reaction and the high selectivity to 1-Phenylethanone. restriction.
For example, Japanese Laid-Open Patent publication No. 2008-0156347 is disclosed and prepares benzene using load type palladium catalyst
The novel method of ethyl ketone.Although the method can guarantee reaction yield to a certain extent, mineral acid such as hydrochloric acid and
Analog should be added after pyroreaction is carried out during room temperature reaction, so as to cause complicated process of preparation, reaction
Time is long, and needs the monomer (reactant) of costliness, so as to reduce business efficiency.
Additionally, Japanese Laid-Open Patent publication No. 1997-188647 is disclosed being prepared using ethanol or bromo ethyl phenenyl
The method of 1-Phenylethanone., Qi Zhong phosphonium salts or ammonium salt are used as catalyst.However, the method further relate to complexity preparation process or should
Through multiple steps, and including through 2 hours or the step of more than 2 hours, the bromine by 2.5 equivalents dropped to ethylo benzene, so as to drop
Low production efficiency.
Additionally, Japanese Laid-Open Patent publication No. 2008-44858 is disclosed use acetonitrile in the presence of palladium catalyst
The method for synthesizing 1-Phenylethanone. with the mixed solvent of water.However, the method is uneconomic, because needing in reaction number of types of
Material, and reaction should be lasted about 16 hours in a nitrogen atmosphere, so as to cause process time length and complication.
Additionally, Japanese Laid-Open Patent publication No. 1993-309431 is disclosed in heavy metal catalyst and halo
By the oxidation reaction of ethylo benzene in the presence of quaternary ammonium salt or halo quaternary alkylphosphonium salts of promoter such as halo and the like
The method for preparing 1-Phenylethanone..However, according to the method, ethylo benzene is added to organic acid in promoter and heavy metal catalyst
Add after medium, and temperature is increased to into 100 DEG C or higher, so as to cause complicated process of preparation, and according to use
Promoter, the selectivity of the conversion ratio of reactant or final synthetic product is not enough.
Detailed description of the invention
Technical problem
It is an object of the invention to provide method of the simplified technique to synthesize 1-Phenylethanone. in high yield can be passed through.
Technical scheme
According to the present invention, there is provided the method for preparing 1-Phenylethanone., methods described is included in selected from based on imidoization
Compound, alkali compoundss and water composition group at least one compound and comprising at least cobalt as active component catalyst
In the presence of compound, in the organic solvent comprising organic acid the step of ethyl oxide benzene.
In the preparation method of 1-Phenylethanone., oxidation reaction can based on imido compound, alkali compoundss, water or
In the presence of alkali compoundss and water and catalyst compounds, carry out in the organic solvent comprising organic acid.
In the preparation method of 1-Phenylethanone., oxidation reaction can comprising cobalt as active component catalyst compounds with
And based in the presence of imido compound, carry out in the organic solvent comprising organic acid.
Herein, can be included at the nitrogen-atoms of imide by reactive functional groups based on imido compound
Substituted imide compound.
In the preparation method of 1-Phenylethanone., oxidation reaction can include the catalyst of cobalt, manganese and bromine as active component
In the presence of compound and alkali compoundss, carry out in the organic solvent comprising organic acid.
Herein, alkali compoundss can be at least one compound selected from group consisting of：Sodium carbonate, hydrogen
Sodium oxide, sodium pyrophosphate, potassium carbonate, potassium hydroxide and potassium pyrophosphate.
In the preparation method of 1-Phenylethanone., oxidation reaction can include the catalyst of cobalt, manganese and bromine as active component
In the presence of compound and water, carry out in the organic solvent comprising organic acid.
In the preparation method of 1-Phenylethanone., oxidation reaction can include the catalyst of cobalt, manganese and bromine as active component
In the presence of compound and alkali compoundss and water, carry out in the organic solvent comprising organic acid.
Can be with 2 carboxylic acids to 20 carbon numbers comprising organic acid in organic solvent.
Oxidation reaction can be carried out by making oxygen-containing gas be contacted with ethylo benzene.Additionally, oxidation reaction can be in 5 bars extremely
Carry out at a temperature of 50 DEG C to 250 DEG C under the pressure of 75 bars.
Beneficial effect
The preparation method of the 1-Phenylethanone. that the present invention is provided shows the high selectivity to 1-Phenylethanone., while with high raw material
Compound conversion ratio such that it is able to realize producing 1-Phenylethanone. in enormous quantities by simplified technique.Additionally, the preparation method can be in temperature
Carry out with conditions of, so as to minimize the corrosion of synthesis device, and allow selectivity to be carried out by eco-friendly technique
Oxidation, and not use environment pollutant.
Specific embodiment
Hereinafter, the preparation method of the 1-Phenylethanone. of specific embodiment of the invention will be explained.
First, terminology used herein is used for the purpose of mentioning specific embodiment, and is not intended to limit this
It is bright.Singulative used herein includes its plural form, unless which has clearly contrary implication." including " used herein
Or the implication of "comprising" embodies specific character, region, entirety, step, operation, key element or composition, and it is not excluded for adding which
Its specific character, region, entirety, step, operation, key element or composition.
According to the present invention, there is provided the method for preparing 1-Phenylethanone., methods described is included in selected from based on imidoization
Compound, alkali compoundss and water composition group at least one compound and comprising at least cobalt as active component catalyst
In the presence of compound, in the organic solvent comprising organic acid the step of ethyl oxide benzene.
The preparation method of 1-Phenylethanone. provided by the present invention is the method for synthesizing 1-Phenylethanone. by the oxidation reaction of ethylo benzene,
Ethylo benzene is relatively cheap starting compound.
However, as shown in following chemical formula 1, in the oxidation reaction of ethylo benzene, according to reaction process, can produce
Various compounds in addition to 1-Phenylethanone., such as phenol, benzoic acid, 1- phenylethanols, benzaldehyde, styrene and the like.
[chemical formula 1]
Therefore, in order to improve the reaction efficiency for synthesizing 1-Phenylethanone. by the oxidation reaction of ethylo benzene, substantially, raw material chemical combination
The conversion ratio of thing ethylo benzene should be it is high, and to 1-Phenylethanone. provide high selectivity be particular importance.
However, the preparation method of the 1-Phenylethanone. of the hitherto known oxidation reaction by ethylo benzene has low ethyl
Benzene conversion ratio, or the low selectivity to 1-Phenylethanone., and so as to can not meet two above requirement simultaneously.
Additionally, generally, in the oxidation of ethylo benzene, if reaction temperature is low, preparation time may become longer, so as to
Long-time is exposed to heat, and this reduces reaction yield, and if conversely, reaction temperature is high, by-product is because of high temperature
It is a large amount of to produce, cause which to be difficult to obtain the 1-Phenylethanone. with high-purity or high selectivity.
Conversely, the preparation method of the 1-Phenylethanone. of the present invention selected from based on imido compound, alkali compoundss and
At least one compound of the group of water composition is together with comprising entering in the presence of at least catalyst compounds of the cobalt as active component
The oxidation reaction of row ethylo benzene, so as to obtain the 1-Phenylethanone. with high selectivity, while with high ethylbenzene conversion.This
Outward, synthesize 1-Phenylethanone. by methods described to realize by a simplified technique, and which can be relatively mild
Under the conditions of carry out, so as to reduce the concern of the corrosion with regard to synthesis device.
Specifically, due at least one selected from the group constituted based on imido compound, alkali compoundss and water
Compound is used in the oxidation step of ethylo benzene, it is possible to is guaranteed high reaction yield, and is not risen high-temperature, and especially
Ground, it is possible to obtain the 1-Phenylethanone. with high selectivity.
Seem, selected from least one chemical combination of the group constituted based on imido compound, alkali compoundss and water
Thing is conducive to the formation of free radical, so as to the work of catalyst compounds being even modified in low temperature range in oxidation reaction
Property.
Also seem, these compounds serve as selective reaction inhibitor, so as to suppress in the oxidizing process of ethylo benzene
The generation of the by-product (mainly, acid compound) in addition to 1-Phenylethanone..
So, the oxidation reaction of ethylo benzene can be selected from based on imido compound, alkali compoundss and water group
Into group at least one compound and comprising carrying out in the presence of catalyst compounds of at least cobalt as active component.
Herein, can be with the gross weight of the organic solvent in the oxidation reaction based on ethylo benzene and for ethylo benzene
1500ppmw to 20,000ppmw, or 2000ppmw to 10,000ppmw, or 2500ppmw to 7,500ppmw content addition base
In imido compound.Specifically, it is advantageous that used based on imido compound with 1500ppmw or more contents,
To guarantee the conversion ratio of ethylo benzene and to exceed optimum level to the selectivity of 1-Phenylethanone..If however, too much using being based on
Imido compound, then oxidation reaction may be suppressed on the contrary, and the selectivity to 1-Phenylethanone. may be reduced.Therefore, have
Profit is to use imide compound with 20,000ppmw or less content.
According to the present invention, the instantiation based on imido compound can be included in quilt at the nitrogen-atoms of imide
Reactive functional groups replace based on imido compound.Herein, the example of reactive functional groups can include hydroxyl,
Acetoxyl group, carboxyl and the like, and preferably, which can be hydroxyl.
At least one selected from group consisting of can be included based on the more specifically example of imido compound
Compound：HP, N- hydroxysuccinimides, N- hydroxyl -1,8- naphthalimides, N- acetoxyl groups -
Phthalimide, trihydroxy-imino group-cyanuric acid, N- hydroxy maleimides, N- hydroxy chlorides are sub- for phthalyl
Amine, N- hydroxy chlorides are for naphthalimide and N- hydroxyl nitrophthalimides.
Furthermore, it is possible to the gross weight of the organic solvent in the oxidation reaction based on ethylo benzene and for ethylo benzene
0.1ppmw to 70ppmw, or 1ppmw to 70ppmw, or 1ppmw to 50ppmw, or 1ppmw to 45ppmw, or 5ppmw is extremely
45ppmw or 1ppmw to 35ppmw, or 5ppmw to 30ppmw basic ion concentration addition can be used for ethylo benzene oxidation it is anti-
Alkali compoundss in answering.Specifically, it is advantageous that with the basic ion concentration of 0.1ppmw or bigger include alkali compoundss, with
Just fully show the effect caused by the addition of alkali compoundss.If however, using alkali compoundss too much, which can
There can be detrimental effect to the activity of catalyst compounds, the selectivity of 1-Phenylethanone. may be reduced, and oxidation time
May become longer, so as to increase by-product.It would thus be advantageous to include alkalization with the basic ion concentration of 70ppmw or less
Compound.
The instantiation of alkali compoundss can include at least one compound selected from group consisting of：Carbonic acid
Sodium, sodium hydroxide, sodium pyrophosphate, potassium carbonate, potassium hydroxide and potassium pyrophosphate.
Furthermore, it is possible to the gross weight of the organic solvent in the oxidation reaction based on ethylo benzene and for ethylo benzene
10ppmw to 50,000ppmw, or 100ppmw to 30,000ppmw, or the content addition of 1000ppmw to 20,000ppmw can be with
For the water in the oxidation reaction of ethylo benzene.
I.e., it is advantageous that include water with 10ppmw or more contents, so that the addition that fully shows by water is caused
Effect.However, if water is more than being necessarily included in response system, oxidation reaction may be suppressed to reduce ethylo benzene
Conversion ratio.It would thus be advantageous to include water with 50,000ppmw or less content.
Herein, selected from least oneization of the group constituted based on imido compound, alkali compoundss and water
Compound can be with various combination applications in the oxidation reaction of ethylo benzene.Specifically, these compounds separately can be used for
The oxidation reaction of ethylo benzene；Or its two or more, such as based on imido compound and alkali compoundss, sub- based on acyl
The compound and water of amine, alkali compoundss and water and it is based on imido compound and alkali compoundss and water can be together
Use.Especially, according to an embodiment, if alkali compoundss and water are used for the oxidation reaction of ethylo benzene together, can
To obtain 1-Phenylethanone. compared with high selectivity.
Meanwhile, the oxidation reaction of ethylo benzene is entered in the presence of comprising at least catalyst compounds of the cobalt as active component
OK.
Herein, catalyst compounds can serve as the main catalytic of the overall reaction rate for including oxidation reaction for raising
Agent.
, comprising at least cobalt as active component, catalyst compounds can also be comprising its in addition to cobalt for catalyst compounds
Its active component, and the species of active component can change according to compound present in response system.
For one embodiment, if the oxidation reaction for ethylo benzene being applied to based on imido compound, is catalyzed
Immunomodulator compounds can show high ethylbenzene conversion and the high selectivity to 1-Phenylethanone., and not include other work in addition to cobalt
Property composition.That is, an embodiment of the invention, oxidation reaction can include catalyst of the cobalt as active component
Compound and based in the presence of imido compound, is carried out in the organic solvent comprising organic acid.
For an alternative embodiment, if alkali compoundss or water to be applied to the oxidation reaction of ethylo benzene, may have
Profit, catalyst compounds also comprising the manganese and bromine in addition to cobalt as active component, to guarantee high ethylbenzene conversion
Rate and the high selectivity to 1-Phenylethanone.,.
That is, another embodiment of the invention, oxidation reaction can include cobalt, manganese and bromine as active component
In the presence of catalyst compounds and alkali compoundss, carry out in the organic solvent comprising organic acid.
Additionally, another embodiment of the invention, oxidation reaction can comprising cobalt, manganese and bromine as active component
Catalyst compounds and water in the presence of, comprising organic acid organic solvent in carry out.
Additionally, according to another embodiment, oxidation reaction can include the catalyst of cobalt, manganese and bromine as active component
In the presence of compound and alkali compoundss and water, carry out in the organic solvent comprising organic acid.
With regard to the active component being included in catalyst compounds, cobalt and manganese can be in the form of its slaines or hydrate
Included, and bromine can be included as the acid.Herein, slaine can include inorganic salt or organic salt, and
Its instantiation can include sulfate, nitrate, hydrochlorate and with 2 carboxylates to 20 carbon numbers.Carboxylic acid includes fat
Aliphatic carboxylic acid and aromatic carboxylic acid, and its instantiation can include acetic acid, butanoic acid, Palmic acid, oxalic acid, propanoic acid, benzoic acid
And the like.
The concentration of the active component being included in catalyst compounds can be according to the oxidation reaction speed of ethylo benzene and right
The selectivity of 1-Phenylethanone. and similar adjusting.
For example, can be with the gross weight of the organic solvent in the oxidation reaction based on ethylo benzene and for ethylo benzene
5ppmw to 300ppmw, or 10ppmw to 200ppmw, or the content of 20ppmw to 100ppmw come comprising cobalt.
If additionally, comprising other active component in addition to cobalt, could be with based on the total of organic solvent and ethylo benzene
The 50ppmw to 500ppmw of weight, or 80ppmw to 300ppmw content include manganese；And can be with based on organic solvent and second
The content of the 50ppmw to 800ppmw or 100ppmw to 400ppmw of the gross weight of base benzene includes bromine.
I.e., it is advantageous to active component of the catalyst comprising off-limits lower limit, so that the oxidation for guaranteeing ethylo benzene is anti-
Answer speed and conversion ratio.If however, active component is included in catalyst compounds too much, fast due to oxidation reaction
Speed progress, it may be difficult to control selections oxidation reaction, and so as to reduce to the selectivity of 1-Phenylethanone..Therefore, favorably
, catalyst compounds are included in the active component below the upper limit of scope.
Meanwhile, the oxidation reaction of ethylo benzene can be carried out using the organic solvent comprising organic acid, or which can have
Carry out in machine solvent.
Herein, organic solvent can be comprising with 10wt% or more, or the organic acid of 50wt% or more contents,
And which can comprise only machine acid.
Can be with the acid acid of 2 to 20 carbon numbers comprising organic acid in organic solvent.Carboxylic acid can include fat
Aliphatic carboxylic acid or aromatic carboxylic acid, and its instantiation can include acetic acid, butanoic acid, Palmic acid, oxalic acid, propanoic acid, benzoic acid
And the like.
Additionally, the amount of organic solvent can consider the efficiency of oxidation reaction and be similar to determine.As non-limiting reality
Example is applied, can be with 1 based on ethylo benzene:5 to 1:50th, or 1:5 to 1:30th, or 1:5 to 1:25 weight ratio uses organic solvent.
The oxidation reaction of ethylo benzene can be carried out by making oxygen-containing gas be contacted with ethylo benzene.Herein, it is oxygenous
Body can be comprising 10vol% or more, or 20vol% or more, or 50vol% or more oxygen, and surpluses is lazy
Property gas.Oxygen-containing gas can only include oxygen.Used as non-limiting example, the oxidation that air can be used for ethylo benzene is anti-
Should.
The oxidation reaction of ethylo benzene can be carried out under the pressure of 5 bars to 75 bars or 10 bars to 50 bars.I.e., it is advantageous to
Oxidation reaction is carried out under the pressure of 5 bars or bigger, to be sufficiently carried out oxidation reaction.Simultaneously as oxidation pressure
It is higher, so response speed may increase.However, in order to meet condition of high voltage, facility may be caused to limit and equipment cost increasing
Plus.It is therefore advantageous that oxidation reaction is carried out under the pressure of 75 bars or less.
The oxidation reaction of ethylo benzene can 50 DEG C to 250 DEG C, or 70 DEG C to 220 DEG C, or 100 DEG C to 200 DEG C, or 110
DEG C carry out at a temperature of 150 DEG C.That is, if oxidizing reaction temperature is low, response speed may be reduced or yield may be reduced.
If conversely, oxidizing reaction temperature is too high, being likely difficult to control response speed, so as to increasing by-product and reducing to benzene second
The selectivity of ketone.
The time for carrying out the oxidation reaction of ethylo benzene can consider volume of production of reaction yield and by-product and the like
To determine, and so as to not be specifically limited.Used as non-limiting example, the oxidation reaction of ethylo benzene can carry out continuing
30 minutes to 10 hours, or 1 hour to 8 hours, or 2 hours to 5 hours.
The oxidation reaction of ethylo benzene can be carried out under the stirring of reactant, to improve reaction efficiency.Herein, stir
Mix speed (although not specifically limit) can be advantageously controlled for 10rpm to 1000rpm, or 150rpm to 750rpm, or
200rpm to 500rpm, to improve reaction efficiency.
Hereinafter, there is provided preferred embodiment is helping understand the present invention.However, these embodiments only for illustration this
It is bright, and the scope of the present invention not limited to this.
In following embodiment and comparing embodiment, the component analyses of the product of oxidation reaction are detected using flame ionization
Device is carried out using gas chromatography.Based on the result of component analyses, the conversion ratio (=[ethylo benzene being initially charged into of ethylo benzene
Content-content comprising ethylo benzene in the product]/[content of the ethylo benzene being initially charged into] * 100) and to 1-Phenylethanone.
Selectivity (=1-Phenylethanone. percentage composition in the reaction product) is calculated and is respectively displayed in table 1 below and table 2
In.
Embodiment 1-1
By ethylo benzene and acetic acid with 1:19 weight is than being incorporated in the 500ml high-pressure reactors equipped with agitator.This
Outward, by the four acetate hydrate cobalt (Co (CH of the 80ppmw based on Co concentration3COO)2·4H2O), and 5000ppmw N- hydroxyls
Phthalimide is incorporated in reactor.The inner utilization nitrogen atmosphere displacement of high-pressure reactor, supplies the sky of about 30 bars
Gas, and and then, the temperature of reactor is increased to about 130 DEG C to carry out oxidation reaction.Herein, mixing speed is in oxidation
400rpm is maintained at during reaction, and is reacted till no pressure change.After oxidation reaction is completed, instead
Answer the inside of device to be cooled to room temperature, and and then obtain the product comprising 1-Phenylethanone..
Embodiment 1-2
N- hydroxyl of the product comprising 1-Phenylethanone. by obtaining with embodiment 1-1 identical method, except adding 5000ppmw
Outside the HP of base succimide rather than 5000ppmw.
Embodiment 1-3
N- hydroxyl of the product comprising 1-Phenylethanone. by obtaining with embodiment 1-1 identical method, except adding 5000ppmw
Outside the HP of base -1,8- naphthalimides rather than 5000ppmw.
Embodiment 1-4
N- hydroxyl of the product comprising 1-Phenylethanone. by obtaining with embodiment 1-1 identical method, except adding 2000ppmw
Outside the HP of base -1,8- naphthalimides rather than 5000ppmw.
Embodiment 1-5
N- hydroxyl of the product comprising 1-Phenylethanone. by obtaining with embodiment 1-1 identical method, except adding 3000ppmw
Outside the HP of base -1,8- naphthalimides rather than 5000ppmw.
Embodiment 1-6
N- hydroxyl of the product comprising 1-Phenylethanone. by obtaining with embodiment 1-1 identical method, except adding 4000ppmw
Outside the HP of base -1,8- naphthalimides rather than 5000ppmw.
Comparing embodiment 1
Product comprising 1-Phenylethanone. by with embodiment 1-1 identical method obtain, except respectively addition based on Co it is dense
The four acetate hydrate cobalt (Co (CH of the 80ppmw of degree3COO)2·4H2O), based on Mn concentration 160ppmw four acetate hydrate manganese
(Mn(CH3COO)2·4H2The hydrogen bromide (HBr) rather than four acetate hydrate cobalts of the 200ppmw O) and based on Br concentration is used as urging
Agent compound and carry out oxidation reaction and without HP outside.
Comparing embodiment 2
Product comprising 1-Phenylethanone. by with embodiment 1-1 identical method obtain, except addition based on Ru concentration
Three chloride hydrate ruthenium (the III) (RuCl of 800ppmw3·3H2O) rather than four acetate hydrate cobalts as catalyst compounds and
Carry out oxidation reaction and without HP outside.
Table 1
In table 1, " AP " represents 1-Phenylethanone., and " BA " represents benzoic acid, and " PE " represents 1- phenylethanols, and " other " table
Show the remaining compound in addition to AP, BA and PE.
As can be seen from Table 1, confirmation, relative to comparing embodiment 1 and comparing embodiment 2, embodiment 1-1 is extremely
Embodiment 1-6 shows high ethylbenzene conversion, and especially shows on the selectivity to 1-Phenylethanone. dramatically different.Its
In, although embodiment 1-1 and embodiment 1-2 are with the ethylbenzene conversion similar to comparing embodiment 1 and comparing embodiment 2,
But which shows dramatically different on the selectivity to 1-Phenylethanone..Additionally, wherein using the ratio of different types of catalyst compounds
There is low ethylbenzene conversion compared to embodiment compared with embodiment 2, and also with the low selectivity to 1-Phenylethanone., so as to true
Recognize poor reaction efficiency.
Embodiment 2-1
By ethylo benzene and acetic acid with 1:19 weight is than being incorporated in the 500ml high-pressure reactors equipped with agitator.This
Outward, by the four acetate hydrate cobalt (Co (CH of the 80ppmw based on Co concentration3COO)2·4H2O), the 160ppmw based on Mn concentration
Four acetate hydrate manganese (Mn (CH3COO)2·4H2The hydrogen bromide (HBr) of the 200ppmw O) and based on Br concentration is respectively incorporated into
In reactor, the sodium carbonate of the 10ppmw based on Na concentration is subsequently introduced.The inner utilization nitrogen atmosphere displacement of high-pressure reactor,
The air of about 30 bars of supply, and the temperature of reactor is increased to about 130 DEG C to carry out oxidation reaction.Herein, stir
Speed is maintained at 400rpm during oxidation reaction, and is reacted till no pressure change.In oxidation reaction
After completing, the inside of reactor is cooled to room temperature, and and then obtains the product comprising 1-Phenylethanone..
Embodiment 2-2
Product comprising 1-Phenylethanone. by with embodiment 2-1 identical method obtain, except sodium carbonate (is based on 25ppmw
Na concentration) amount addition outside.
Embodiment 3-1
By ethylo benzene and acetic acid with 1:19 weight is than being incorporated in the 500ml high-pressure reactors equipped with agitator.This
Outward, by the four acetate hydrate cobalt (Co (CH of the 80ppmw based on Co concentration3COO)2·4H2O), the 160ppmw based on Mn concentration
Four acetate hydrate manganese (Mn (CH3COO)2·4H2The hydrogen bromide (HBr) of the 200ppmw O) and based on Br concentration is respectively introduced
To in reactor, the water of 5000ppmw is subsequently introduced.The inner utilization nitrogen atmosphere displacement of high-pressure reactor, supplies about 30 bars
Air, and and then be increased to about 130 DEG C to carry out oxidation reaction by the temperature of reactor.Herein, mixing speed is in oxygen
400rpm is maintained at during changing reaction, and is reacted till no pressure change.After oxidation reaction is completed,
The inside of reactor is cooled to room temperature, and and then obtains the product comprising 1-Phenylethanone..
Embodiment 3-2
Product comprising 1-Phenylethanone. by with embodiment 3-1 identical method obtain, except add 8000ppmw water when
Carry out outside oxidation reaction.
Embodiment 3-3
Water of the product comprising 1-Phenylethanone. by obtaining with embodiment 3-1 identical method, except adding 10,000ppmw
Outside Shi Jinhang oxidation reactions.
Embodiment 4-1
Product comprising 1-Phenylethanone. by with embodiment 2-1 identical method obtain, except by the water of 8000ppmw in addition
Carry out outside oxidation reaction when being added to reactor.
Embodiment 4-2
Product comprising 1-Phenylethanone. is by obtaining with embodiment 2-1 identical method, (dense based on Na except adding 25ppmw
Degree) sodium carbonate and carry out outside oxidation reaction when adding the water of 8000ppmw.
Table 2
In table 2, " AP " represents 1-Phenylethanone., and " BA " represents benzoic acid, and " PE " represents 1- phenylethanols, and " other " table
Show the remaining compound in addition to AP, BA and PE.
As can be seen from Table 2, confirmation, compared to comparing embodiment 1 and comparing embodiment 2, embodiment 2-1 is extremely
Embodiment 4-2 shows high ethylbenzene conversion, and especially shows on the selectivity to 1-Phenylethanone. dramatically different.This
Outward, although comparing embodiment 1 using with the catalyst compounds of embodiment identical type because oxidation reaction carried out without
Addition alkali compoundss and water, so ethylbenzene conversion is relatively low, and the selectivity to 1-Phenylethanone. is significantly reduced.
Claims (7)
1. a kind of method for preparing 1-Phenylethanone., is included in based on imido compound and comprising cobalt as active component
Catalyst compounds in the presence of, comprising with 2 carboxylic acids to 20 carbon numbers organic solvent in ethyl oxide benzene,
Wherein described is at least one compound selected from group consisting of based on imido compound：N- hydroxyl -1,
8- naphthalimides and N- hydroxy chlorides for naphthalimide,
The active component of wherein described catalyst is at least one compound selected from group consisting of：Cobalt nitrate,
Cobaltous sulfate, hydrochloric acid cobalt, the carboxylic acid cobalt with 2 to 20 carbon numbers and its hydrate,
It is wherein described based on imido compound with the 1500ppmw of the gross weight based on the organic solvent and ethylo benzene extremely
The amount of 20,000ppmw is present.
2. method according to claim 1, wherein the catalyst compounds are comprising based on the organic solvent and described
The cobalt of the 5ppmw to 300ppmw of the gross weight of ethylo benzene is used as active component.
3. method according to claim 1, wherein the organic solvent is with based on ethylo benzene 1:5 to 1:50 weight ratio quilt
Use.
4. method according to claim 1, wherein oxidation reaction are carried out by making oxygen-containing gas be contacted with ethylo benzene.
5. method according to claim 1, wherein oxidation reaction are carried out under the pressure of 5 bars to 75 bars.
6. method according to claim 1, wherein oxidation reaction are carried out at a temperature of 50 DEG C to 250 DEG C.
7. method according to claim 1, wherein oxidation reaction are carried out when being stirred with 10rpm to 1000rpm.
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