CN115636738B - Method for preparing diphenyl ketone from diphenyl methane - Google Patents
Method for preparing diphenyl ketone from diphenyl methane Download PDFInfo
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 title claims abstract description 63
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 81
- 238000003756 stirring Methods 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 90
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- -1 peroxide tert-butyl hydroperoxide Chemical class 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 56
- 239000000203 mixture Substances 0.000 description 30
- 238000001514 detection method Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- 239000007791 liquid phase Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CIVCELMLGDGMKZ-UHFFFAOYSA-N 2,4-dichloro-6-methylpyridine-3-carboxylic acid Chemical compound CC1=CC(Cl)=C(C(O)=O)C(Cl)=N1 CIVCELMLGDGMKZ-UHFFFAOYSA-N 0.000 description 1
- WAASLNJSONWCGI-UHFFFAOYSA-N 4,4-dicyclohexylpiperidine Chemical compound C1(CCCCC1)C1(CCNCC1)C1CCCCC1 WAASLNJSONWCGI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GIJXKZJWITVLHI-PMOLBWCYSA-N benzatropine Chemical compound O([C@H]1C[C@H]2CC[C@@H](C1)N2C)C(C=1C=CC=CC=1)C1=CC=CC=C1 GIJXKZJWITVLHI-PMOLBWCYSA-N 0.000 description 1
- 229960001081 benzatropine Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000525 diphenhydramine hydrochloride Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing diphenyl ketone from diphenyl methane, belonging to the technical field of organic synthesis; in the invention, peroxide is used as an oxidant, and a nitrogen doped carbon nano tube is used as a catalyst in a solvent system to perform oxidation reaction of diphenyl methane, so as to obtain diphenyl ketone. The invention takes peroxide tert-butyl hydroperoxide as oxidant to react under normal pressure, thereby effectively improving the safety of the reaction and reducing the operation difficulty of the reaction. According to the invention, the nitrogen content and the nitrogen consumption of the catalyst nitrogen-doped carbon nano tube are regulated, so that the yield is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing diphenyl ketone from diphenyl methane.
Background
The diphenyl ketone is an important fine chemical and medical intermediate, has very wide application, and can be used for producing important chemical products such as ultraviolet absorbers, organic pigments, fragrances, pesticides and the like. In the aspect of medicine, the diphenyl ketone can be used for producing medicines such as dicyclohexyl piperidine, benzatropine hydrobromide, diphenhydramine hydrochloride and the like. In addition, diphenyl ketone itself can be used widely as an important styrene polymerization inhibitor and perfume fixative in various perfumes and soap fragrances. Therefore, it is important to find a method capable of synthesizing diphenyl ketone efficiently and stably.
The diphenyl methane is used as a reactant, and the alpha-carbon of the diphenyl methane is catalyzed and oxidized to form carbonyl, so that the diphenyl ketone is obtained effectively. Marwah et al (US 6274746) propose that diphenyl ketone can be prepared by slowly dropwise adding sodium hypochlorite solution under the reaction condition of 0-5 ℃ by taking diphenyl methane as a raw material, tert-butyl hydroperoxide as an oxidant and ethyl acetate as a solvent. Ji Gongbing et al (CN 104478677B) propose that the conversion of diphenylmethane is between 2 and 47% with diphenylmethane as the starting material, metalloporphyrin as the catalyst, and oxygen of 0.2-2.0MPa as the catalyst, at a reaction temperature of 50-150 ℃. Liu et al (Nano Research,2021,14 (9): 3260-3266) reported that the yield of diphenyl ketone could reach 13% after reaction for 12 hours by introducing 10atm of oxygen into the reaction system using composite nanospheres loaded with gold nanoparticles as catalysts. Zhang et al (Journal of Molecular Structure,2021, 1233:130043) reported that the reaction of diphenyl methane was catalyzed by gold ion complexes as the catalyst and t-butyl hydroperoxide as the oxidant at 90℃for 18h, with yields of diphenyl ketone between 30% and 80% under different solvent conditions. Kimberley et al (Angewandte Chemie International Edition,2021,60 (28): 15243-15247) reported a yield of diphenyl ketone of 40% at 65℃for 24 hours with metal-organic framework material MFM-170 as catalyst, t-butyl hydroperoxide as oxidant, and acetonitrile as solvent.
The above documents illustrate that the method of oxidizing diphenylmethane to diphenyl ketone is feasible, but the literature method still has various disadvantages, such as using sodium hypochlorite solution and tert-butyl hydroperoxide mixed solution as an oxidizing agent, reacting to release a large amount of heat, easily generating side reactions and making the reaction conditions difficult to control. The use of high pressure oxygen as the oxidant presents a certain risk and high operational difficulties. The noble metal or the oxide and the complex thereof are used as the catalyst, the limited reserve and the high price of the noble metal can lead to the increase of the cost in the production process, and the metal ions in the reaction system can bring new problems to sewage treatment and environmental protection. While the synthesis of the metal-organic framework material itself is still in progress, this results in some immaturity in the synthesis of the material, and stability of the metal-organic framework material is also a significant challenge. Aiming at the problems, the production process for generating the diphenyl ketone by oxidizing the diphenyl methane, which has the advantages of high safety, simple and convenient operation, greenness, high efficiency and suitability for industrial production, is provided with great significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for preparing diphenyl ketone from diphenyl methane; realizing the efficient preparation of diphenyl ketone by using tert-butyl hydroperoxide as an oxidant and oxidizing diphenyl methane. The invention discloses an economical, green and reliable method for synthesizing diphenyl ketone by using a nitrogen-doped carbon nano tube which is simple to prepare and environment-friendly as a catalyst.
The technical scheme adopted by the invention is as follows:
a method for preparing diphenyl ketone from diphenyl methane, comprising the following steps:
in a solvent system, peroxide is used as an oxidant, and nitrogen doped carbon nano tubes are used as catalysts to perform oxidation reaction of diphenyl methane.
Preferably, the nitrogen content of the nitrogen-doped carbon nanotube is 0.5 to 5wt%.
Further preferably, the nitrogen content of the nitrogen-doped carbon nanotubes is 0.5 to 2.5wt%.
Preferably, the preparation method of the nitrogen-doped carbon nanotube comprises the following steps: and under the protective atmosphere, the carbon nano tube reacts with the mixed solution of pyridine and cyclohexane or pyridine at 600-800 ℃ to obtain the nitrogen doped carbon nano tube.
Further preferably, the volume ratio of the pyridine to the mixed solution in the mixed solution of the pyridine and the cyclohexane is 0.1-1: 1, and is not 1; the mass volume ratio of the carbon nano tube to the mixed solution of pyridine and cyclohexane or pyridine is 0.05g: 0.5-3 ml;
further preferably, the protective atmosphere is argon.
Preferably, the temperature of the oxidation reaction is 30-70 ℃.
Further preferably, the temperature of the oxidation reaction is 50 to 70 ℃.
Preferably, the solvent is at least one of acetonitrile, 1, 2-dichloroethane, toluene and ethyl acetate.
Further preferably, the solvent is acetonitrile.
Preferably, the volume mass ratio of the solvent to the diphenylmethane is 5-20ml:1g.
Preferably, the mass ratio of the nitrogen-doped carbon nano tube to the diphenylmethane is 0.01-0.05: 1.
further preferably, the mass ratio of the nitrogen-doped carbon nanotubes to the diphenylmethane is 0.01-0.025: 1.
preferably, the peroxide is t-butyl hydroperoxide; the molar ratio of the peroxide to the diphenylmethane is 0.5-3: 1.
further preferably, the molar ratio of the peroxide to the diphenylmethane is 1.5 to 3:1.
preferably, the time of the oxidation reaction is 0.5 to 9 hours.
Further preferably, the time of the oxidation reaction is 1 to 9 hours.
Preferably, the oxidation reaction is carried out under stirring at a rate of 300 to 900rpm.
Further preferably, the stirring rate is 600 to 900rpm.
Compared with the prior art, the invention has the following advantages:
1) The invention takes tert-butyl hydroperoxide as oxidant to react under normal pressure, thereby effectively improving the safety of the reaction and reducing the operation difficulty of the reaction.
2) The method takes the nitrogen-doped carbon nano tube which is green and environment-friendly and is simple to separate as the catalyst, has excellent environment-friendliness, and can separate and recycle the catalyst easily after the reaction.
3) The nitrogen-doped carbon nanotube prepared by the subsequent doping method can regulate and control the nitrogen content of the nitrogen-doped carbon nanotube by adjusting the process parameters, and compared with the in-situ nitrogen-doped carbon nanotube, the catalyst has higher activity in the oxidation reaction of the diphenyl methane.
4) The invention regulates the nitrogen content of the nitrogen-doped carbon nano tube, and the catalytic yield of the nitrogen content in a certain range is higher (the yield is reduced when the nitrogen content is too high and too low).
5) The method optimizes the dosage of the nitrogen-doped carbon nano tube, and the dosage of the nitrogen-doped carbon nano tube is higher in catalytic yield (the yield is reduced when the dosage is too high and too low) in a certain range.
Drawings
FIG. 1 is a gas chromatogram of the liquid phase mixture after the reaction in example 5.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the invention is not limited to the examples.
The yield (%) of diphenylmethanone in the following examples was calculated by measuring the absolute amount of the formed substance by Gas Chromatograph (GC) analysis after the completion of the reaction and combining the initial amounts of the reactants. The GC detection adopts an internal standard method, chlorobenzene is used as an internal standard substance, and absolute production of substances is calculated by respectively drawing standard curves corresponding to various substances and combining with the GC detection of reaction liquid.
A method for preparing diphenyl ketone from diphenyl methane, comprising the following steps: adding an oxidant into a reaction system in a reactor in which diphenylmethane, a solvent and a catalyst exist, and stirring and reacting at the normal pressure and the temperature of 30-70 ℃ for 0.5-9 hours to obtain diphenylketone; the oxidant is tert-butyl hydroperoxide, and the catalyst is nitrogen doped carbon nanotube.
The Carbon nanotubes of example 1 were prepared by the following steps (Carbon, 2002,40,2968-2970):
FeMo/Al 2 O 3 The catalyst is spread on a porcelain boat, then the porcelain boat is placed in a tube furnace, the mixture of hydrogen and nitrogen is continuously filled for 30min to activate the catalyst, the temperature of a tube cavity is 700 ℃ under the mixed atmosphere of the hydrogen and the nitrogen, and liquefied petroleum gas is continuously filled into the tube furnace within 130 min. Removing residual FeMo/Al by using concentrated hydrochloric acid after cooling 2 O 3 And (3) the catalyst is used for obtaining the carbon nano tube.
The nitrogen-doped carbon nanotubes of examples 2-25 were prepared by the following method:
spreading 0.05g of the carbon nano tube on a porcelain boat, then placing the porcelain boat in a tube furnace, filling argon gas as a protective gas, heating to 760 ℃ at a heating rate of 5 ℃/min, then injecting a pyridine and cyclohexane mixed solution into the tube furnace at a flow rate of 1.5mL/h by using a syringe pump, stopping injection for a period of time, stopping heating after stopping injection by using the syringe pump for 30min, and naturally cooling to room temperature to obtain the nitrogen-doped carbon nano tube (NCNTs).
The injection time is 1h, the volume ratio of the pyridine to the mixed solution is 0.25, 0.5, 0.75 and 1, and the nitrogen doped carbon nano tube with the nitrogen content of 0.50wt%, 0.82wt%, 1.55wt% and 2.54wt% is obtained. The injection time is 2h, the volume ratio of the pyridine to the mixed solution is 0.67 and 1, and the nitrogen doped carbon nano tube with the nitrogen content of 3.42 weight percent and 4.24 weight percent is obtained. The nitrogen content of the nitrogen-doped carbon nanotube is determined by an elemental analysis method, and is calculated by the sum of the nitrogen content=the mass of nitrogen atoms in the material/the mass of carbon atoms and nitrogen atoms in the material.
Example 1
0.97g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of carbon nanotubes were put into a flask, stirred and heated to 70℃with stirring at 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) were injected, and the reaction was started, and after 9 hours of reaction, the catalyst was separated from the reaction solution using a 0.2 μm filter to give a liquid phase mixture after the reaction, and the yield of diphenylketone was 11.66% as a result of GC detection.
Example 2
1.03g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 0.50 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was carried out for 9 hours, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 14.88% by GC detection.
Example 3
0.96g of diphenylmethane, 0.50g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 0.82 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was carried out for 9 hours, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 21.45% by GC detection.
Example 4
0.97g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount: 1.55 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 25.81% by GC detection.
Example 5
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylketone was 28.71% by GC detection (FIG. 1).
Example 6
0.98g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount: 3.42 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was carried out for 9 hours, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 23.01% by GC detection.
Example 7
0.98g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount: 4.24 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 6.55% by GC detection.
0.98g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount: 4.24 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was carried out for 9 hours, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 20.15% by GC detection.
Example 8
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter after 1 hour of reaction, to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 8.68% by GC detection.
Example 9
0.97g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 60℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 7.27% by GC detection.
Example 10
0.96g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 50℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 6.26% by GC detection.
Example 11
0.99g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 40 ℃ at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was started for 1 hour, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 4.09% by GC detection.
Example 12
0.98g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 30℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 3.34% by GC detection.
Example 13
0.99g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, stirred and heated to 70℃with a stirring rate of 900rpm using 12ml of 1, 2-dichloroethane as a solvent, 3ml of t-butylhydroperoxide (70% aq. Sol.) were injected, and the reaction was started, and after 1 hour of the reaction, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 8.51% by GC detection.
Example 14
0.98g of diphenylmethane, 0.53g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of toluene was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 3.46% by GC detection.
Example 15
0.98g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of ethyl acetate was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, the timing was started, after 1 hour of reaction, the catalyst and the reaction solution were separated by using a 0.2 μm filter, a liquid phase mixture after the reaction was obtained, and the yield of diphenylmethanone was 6.67% by GC detection.
Example 16
1.01g of diphenylmethane, 0.53g of chlorobenzene (internal standard) and 10mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 5.38% by GC detection.
Example 17
0.99g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 50mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, the timing was started, after 1 hour of reaction, the catalyst and the reaction solution were separated by using a 0.2 μm filter, a liquid phase mixture after the reaction was obtained, and the yield of diphenylmethanone was 4.40% by GC detection.
Example 18
1.00g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 0.5ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and counting was started, after 1 hour of reaction, the catalyst was separated from the reaction solution using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 2.75% by GC detection.
Example 19
0.99g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 1.5ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and the timing was started, after 1 hour of reaction, the catalyst was separated from the reaction solution using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 5.38% by GC detection.
Example 20
0.98g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and the reaction was started to time, after 0.5 hour of the reaction, the catalyst was separated from the reaction solution using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 4.78% by GC detection.
Example 21
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, the timing was started, after 3 hours of reaction, the catalyst and the reaction solution were separated by using a 0.2 μm filter, a liquid phase mixture after the reaction was obtained, and the yield of diphenylmethanone was 14.54% by GC detection.
Example 22
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 19.65% by GC detection.
Example 23
0.99g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting to time, the reaction was started for 7 hours, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 24.39% by GC detection.
Example 24
0.99g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 300rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter after 1 hour of reaction, to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 4.63% by GC detection.
Example 25
0.98g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen-doped amount 2.54 wt%) were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70℃at a stirring rate of 600rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after starting the time counting, the catalyst and the reaction solution were separated by using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of diphenylmethanone was 5.67% by GC detection.
The in situ nitrogen doped carbon nanotubes of example 26 were prepared by the following steps (Angewandte Chemie International Edition,2011,50 (17), 3978-3982):
FeMo/Al 2 O 3 The catalyst was spread on a porcelain boat, then placed in a tube furnace, continuously charged with a mixture of hydrogen and nitrogen for 30min to activate the catalyst, and 10mL of aniline was injected into the tube furnace at a flow rate of 3mL/h under an ammonia atmosphere at a tube cavity temperature of 180 ℃. Removing residual FeMo/Al by using concentrated hydrochloric acid after cooling 2 O 3 The catalyst is used for obtaining the in-situ nitrogen doped carbon nano tube. Materials in the literatureThe nitrogen content is measured by X-ray photoelectron spectroscopy, the N/C atomic ratio is 4.5%, and the nitrogen content is 4.99wt%; to reduce the error in the measurement method, the present invention uses elemental analysis to measure the nitrogen content of the material, and the nitrogen content of the in-situ nitrogen-doped carbon nanotube is 4.14wt%, which is equivalent to the nitrogen content in example 7.
Example 26
0.99g of diphenylmethane, 0.53g of chlorobenzene (internal standard) and 25mg of in-situ nitrogen-doped carbon nanotubes were put into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, the timing was started, after 1 hour of reaction, the catalyst and the reaction solution were separated by using a 0.2 μm filter, a liquid phase mixture after the reaction was obtained, and the yield of diphenylketone was 4.76% by GC detection.
As can be seen from examples 1 and 2-26, the yield of the diphenyl ketone prepared by the catalysis of the carbon nano tube doped with nitrogen is obviously improved; as can be seen from examples 7 and 26, the nitrogen-doped carbon nanotubes prepared by the different methods have different catalytic properties, and the nitrogen-doped carbon nanotubes prepared by the post-doping method have higher catalytic activity than the in-situ nitrogen-doped carbon nanotubes; it can be seen from examples 2-7 that the catalytic yields are higher (too high and too low yields are reduced) for a range of nitrogen contents; it can be seen from examples 8, 16 and 17 that the catalytic yield of the nitrogen-doped carbon nanotubes is higher (the yield is reduced when the ratio is too high and too low) within a certain range; the temperature, the type of solvent, the amount of oxidant, the reaction time, the stirring rate, etc. all have an effect on the catalytic yield.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A method for preparing diphenyl ketone from diphenyl methane, which is characterized by comprising the following steps:
in a solvent system, peroxide is used as an oxidant, and nitrogen doped carbon nano tubes are used as catalysts to perform oxidation reaction of diphenyl methane; the peroxide is tert-butyl hydroperoxide;
the nitrogen content of the nitrogen-doped carbon nano tube is 0.5-5wt%; the mass ratio of the nitrogen-doped carbon nano tube to the diphenylmethane is 0.01-0.05: 1, a step of;
the preparation method of the nitrogen-doped carbon nano tube comprises the following steps: and under the protective atmosphere, the carbon nano tube reacts with the mixed solution of pyridine and cyclohexane or pyridine at 600-800 ℃ to obtain the nitrogen doped carbon nano tube.
2. The method for preparing diphenyl ketone from diphenyl methane according to claim 1, wherein: the volume ratio of the pyridine to the mixed solution in the mixed solution of the pyridine and the cyclohexane is 0.1-1: 1, and is not 1; the mass volume ratio of the carbon nano tube to the mixed solution of pyridine and cyclohexane or pyridine is 0.05g: 0.5-3 ml;
the protective atmosphere is argon.
3. The method for preparing diphenyl ketone from diphenyl methane according to claim 1, wherein: the temperature of the oxidation reaction is 30-70 ℃.
4. The method for preparing diphenyl ketone from diphenyl methane according to claim 1, wherein: the solvent is at least one of acetonitrile, 1, 2-dichloroethane, toluene and ethyl acetate; the volume mass ratio of the solvent to the diphenylmethane is 5-20ml:1g.
5. The method for preparing diphenyl ketone from diphenyl methane according to claim 1, wherein: the molar ratio of the peroxide to the diphenylmethane is 0.5-3: 1.
6. the method for preparing diphenyl ketone from diphenyl methane according to claim 1, wherein: the time of the oxidation reaction is 0.5-9 h.
7. The process for preparing diphenyl methanone from diphenyl methane according to any one of claims 1-6, wherein: the oxidation reaction is carried out under the stirring condition, and the stirring speed is 300-900 rpm.
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