CN115636738A - Method for preparing diphenyl ketone from diphenylmethane - Google Patents
Method for preparing diphenyl ketone from diphenylmethane 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 64
- 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 59
- 238000000034 method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 72
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 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 84
- 239000012965 benzophenone Substances 0.000 claims description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 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
- 238000002360 preparation method 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
- 238000006243 chemical reaction Methods 0.000 abstract description 101
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- -1 peroxide tert-butyl hydroperoxide Chemical class 0.000 abstract 1
- 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 31
- 238000004817 gas chromatography Methods 0.000 description 30
- 239000007791 liquid phase Substances 0.000 description 27
- 238000001514 detection method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003556 assay Methods 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
- 239000002304 perfume Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material 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
- 238000003892 spreading Methods 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 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
- 230000015572 biosynthetic process Effects 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
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960000525 diphenhydramine hydrochloride Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 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
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing diphenyl ketone from diphenylmethane, belonging to the technical field of organic synthesis; in a solvent system, the invention takes peroxide as an oxidant and nitrogen-doped carbon nanotubes as a catalyst to carry out oxidation reaction of diphenylmethane, so as to obtain the diphenyl ketone. The invention takes peroxide tert-butyl hydroperoxide as an oxidant, and the reaction is carried out under normal pressure, thereby effectively improving the safety of the reaction and reducing the operation difficulty of the reaction. The invention obviously improves the yield by regulating and controlling the nitrogen content and the dosage of the catalyst nitrogen-doped carbon nano tube.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing diphenyl ketone from diphenylmethane.
Background
The diphenyl ketone is an important fine chemical and pharmaceutical intermediate, has wide application, and can be used for producing important chemical products such as ultraviolet absorbers, organic pigments, perfumes, insecticides and the like. In the aspect of medicine, the diphenyl ketone can be used for producing medicaments such as dicyclohexylpiperidine, benztropine hydrobromide, diphenhydramine hydrochloride and the like. In addition, benzophenone itself can be an important styrene polymerization inhibitor and perfume fixative, and is widely used in various perfumes and soap essences. Therefore, it is important to find a method for efficiently and stably synthesizing benzophenone.
It is effective to obtain benzophenone by catalytically oxidizing alpha-carbon of diphenylmethane as a reactant to produce a carbonyl group. Marwah et al (US 6274746) propose that diphenyl ketone can be prepared by slowly adding sodium hypochlorite solution dropwise under the reaction condition of 0-5 ℃ with diphenylmethane as raw material, t-butyl hydroperoxide as oxidant and ethyl acetate as solvent. The Turkey et al (CN 104478677B) propose that when diphenylmethane is used as a raw material, metalloporphyrin is used as a catalyst, oxygen with the pressure of 0.2-2.0MPa is used as a catalyst, and the reaction temperature is 50-150 ℃, the conversion rate of the diphenylmethane is 2-47%. Liu et al (Nano Research,2021,14 (9): 3260-3266) reported that the yield of diphenyl ketone can reach 13% after 12h of reaction by introducing 10atm of oxygen into the reaction system with composite nanospheres loaded with gold nanoparticles as a catalyst. Zhang et al (Journal of Molecular Structure,2021, 1233. Kimberley et al (Angewandte Chemie International Edition,2021,60 (28): 15243-15247) reported a 40% yield of benzophenone over a 24h reaction at 65 ℃ with MFM-170 metal-organic framework material as catalyst, t-butyl hydroperoxide as oxidant, and acetonitrile as solvent.
The above documents show that the oxidation of diphenylmethane to produce benzophenone is feasible, but the literature methods still have various disadvantages, such as the use of a mixed solution of sodium hypochlorite solution and tert-butyl hydroperoxide as an oxidizing agent, the reaction emitting a large amount of heat, the occurrence of side reactions being liable to occur and the difficulty in controlling the reaction conditions. The use of high pressure oxygen as the oxidant has certain risks and high operational difficulties. The noble metal or the oxide and the complex thereof are used as the catalyst, the limited reserves and the high price of the noble metal can cause the cost increase in the production process, and meanwhile, the metal ions in the reaction system can bring new problems to sewage treatment and environmental protection. In the case of metal-organic framework materials, the synthesis method of the material itself is still in a development stage, which results in a certain degree of immaturity in the synthesis of the material, and the stability of the metal-organic framework material is also a great challenge. Aiming at the problems, the production process for generating the diphenyl ketone by oxidizing the diphenylmethane has the advantages of high safety, simple and convenient operation, greenness and high efficiency, and is suitable for industrial production, and has great significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing diphenyl ketone by using diphenylmethane; the method realizes the efficient preparation of the diphenyl ketone by oxidizing the diphenylmethane by using the tert-butyl hydroperoxide as an oxidant. The invention uses the nitrogen-doped carbon nano tube which is simple to prepare and environment-friendly as the catalyst, and invents an economic, green and reliable method for synthesizing the diphenyl ketone.
The technical scheme adopted by the invention is as follows:
a method for preparing diphenyl ketone from diphenylmethane comprises the following steps:
in a solvent system, oxidation reaction of the diphenylmethane is carried out by taking peroxide as an oxidant and nitrogen-doped carbon nano tubes as a catalyst.
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 nanotube is 0.5 to 2.5wt%.
Preferably, the preparation method of the nitrogen-doped carbon nanotube comprises the following steps: under the protective atmosphere, the carbon nano tube reacts with mixed solution of pyridine and cyclohexane or pyridine at the temperature of 600-800 ℃ to obtain the nitrogen-doped carbon nano tube.
More preferably, the volume ratio of pyridine to the mixed solution in the mixed solution of pyridine and cyclohexane is from 0.1 to 1:1, and is not 1; the mass volume ratio of the carbon nano tube to the mixed solution of pyridine and cyclohexane or the pyridine is 0.05g:0.5 to 3ml;
further preferably, the protective atmosphere is argon.
Preferably, the temperature of the oxidation reaction is 30 to 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 of the total weight of the composition.
Preferably, the mass ratio of the nitrogen-doped carbon nanotube to the diphenylmethane is 0.01-0.05: 1.
further preferably, the mass ratio of the nitrogen-doped carbon nanotube to the diphenylmethane is 0.01 to 0.025:1.
preferably, the peroxide is tert-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.
More preferably, the time of the oxidation reaction is 1 to 9 hours.
Preferably, the oxidation reaction is carried out under stirring conditions at a stirring 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 an oxidant, and the reaction is carried out under normal pressure, thereby effectively improving the safety of the reaction and reducing the operation difficulty of the reaction.
2) The invention takes the nitrogen-doped carbon nano tube which is green, environment-friendly and simple to separate as the catalyst, has excellent environment-friendliness, and can separate and recover the catalyst easily after reaction.
3) The nitrogen-doped carbon nanotube prepared by the later doping method can regulate and control the nitrogen content of the nitrogen-doped carbon nanotube by adjusting process parameters, and compared with the in-situ nitrogen-doped carbon nanotube, the catalyst disclosed by the invention has higher activity in a diphenylmethane oxidation reaction.
4) The invention regulates and controls the nitrogen content of the nitrogen-doped carbon nano tube, and the catalytic yield of the nitrogen-doped carbon nano tube is higher within a certain range (the yield is reduced when the nitrogen content is too high or too low).
5) The invention optimizes the dosage of the nitrogen-doped carbon nano tube, and the catalytic yield of the nitrogen-doped carbon nano tube within a certain range is higher (the yield is reduced when the dosage is too high or too low).
Drawings
FIG. 1 is a gas chromatogram of a 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 present invention is not limited to the examples.
The yields (%) of benzophenone in the following examples were calculated by measuring the absolute amounts of the produced substances after the completion of the reaction by Gas Chromatography (GC) analysis and combining the initial amounts of the reactants. And the GC detection adopts an internal standard method, chlorobenzene is used as an internal standard substance, corresponding standard curves of various substances are respectively drawn, and the absolute generation amount of the substances is calculated by combining the GC detection of the reaction liquid.
A method for preparing diphenyl ketone from diphenylmethane comprises the following steps: adding an oxidant into a reaction system in a reactor in which diphenylmethane, a solvent and a catalyst exist, and stirring for reaction under the conditions of normal pressure, the temperature of 30-70 ℃ and the time of 0.5-9 h to obtain the diphenyl ketone; the oxidant is tert-butyl hydroperoxide, and the catalyst is nitrogen-doped carbon nano tube.
The Carbon nanotubes of example 1 were prepared by the following procedure (Carbon, 2002,40, 2968-2970):
FeMo/Al 2 O 3 Spreading on porcelain boat as catalyst, placing in tubular furnace, continuously charging mixture of hydrogen and nitrogen for 30min to activate the catalyst, and continuously introducing liquefied petroleum gas into the tubular furnace at 700 deg.C in the presence of the mixture of hydrogen and nitrogen within 130 min. Removing residual FeMo/Al by using concentrated hydrochloric acid after cooling 2 O 3 And (4) a catalyst to obtain the carbon nano tube.
The nitrogen-doped carbon nanotubes of examples 2 to 25 were prepared by the following method:
and (2) flatly paving 0.05g of the carbon nano tube on a porcelain boat, then placing the porcelain boat in a tube furnace, filling argon as a protective gas, heating to 760 ℃ at the heating rate of 5 ℃/min, injecting the mixed solution of pyridine and cyclohexane into the tube furnace at the flow rate of 1.5mL/h for a period of time by using an injection pump, stopping heating after the injection pump stops injecting 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 to 1, and the nitrogen-doped carbon nano tube with the nitrogen content of 3.42wt percent and 4.24wt percent is obtained. The nitrogen content of the nitrogen-doped carbon nanotube is determined by an element analysis method, and is calculated by the nitrogen content = mass of nitrogen atoms in the material/mass sum of the carbon atoms and the 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 a stirring rate of 900rpm using 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, and after 9 hours of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of benzophenone was 11.66% by GC assay.
Example 2
1.03g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen content 0.50 wt%) were put into a flask, and stirred and heated to 70 ℃ with a stirring rate of 900rpm using 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 9 hours of reaction from the start, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 0.82 wt%) were put into a flask, and stirred and heated to 70 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70 aq. Soln.) was injected thereto, and after 9 hours of reaction from the start, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 21.45% by GC detection.
Example 4
0.97g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotube (nitrogen content 1.55 wt%) were put into a flask, and 12ml of acetonitrile was used as a solvent, and the flask was stirred and heated to 70 ℃ with a stirring rate of 900rpm, and 3ml of t-butyl hydroperoxide (70 aq.
Example 5
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen content 2.54 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, and 3ml of tert-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, and after 9 hours of reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 3.42 wt%) were put into a flask, and stirred and heated to 70 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 9 hours of reaction from the start, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 23.01% by GC assay.
Example 7
0.98g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen content 4.24 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, and 3ml of tert-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction for 1 hour, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 6.55% by GC detection.
0.98g of diphenylmethane, 0.54g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen content 4.24 wt%) were put into a flask, and stirred and heated to 70 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70 aq. Soln.) was injected thereto, and after 9 hours of reaction from the start, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 20.15% by GC detection.
Example 8
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotube (nitrogen content 2.54 wt%) were put into a flask, and 12ml of acetonitrile was used as a solvent, and the flask was stirred and heated to 70 ℃ with a stirring rate of 900rpm, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 60 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 50 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70 aq. Soln.) was injected to start the reaction for 1 hour, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 40 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70 aq. Soln.) was injected thereto, and after 1 hour of the reaction from the start, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of benzophenone was 4.09% by GC assay.
Example 12
0.98g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotubes (nitrogen content 2.54 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred at 900rpm and heated to 30 ℃, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and the reaction was started for 1 hour, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and 12ml of 1, 2-dichloroethane was used as a solvent, the flask was stirred and heated to 70 ℃ with stirring at 900rpm, 3ml of t-butyl hydroperoxide (70 aq. Soln.) was injected, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were charged in a flask, and 12ml of toluene was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, and after 1 hour of the reaction, the catalyst and the reaction liquid were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 70 ℃ at 900rpm with 12ml of ethyl acetate as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and the reaction was started for 1 hour, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 6.67% by GC detection.
Example 16
1.01g of diphenylmethane, 0.53g of chlorobenzene (internal standard) and 10mg of nitrogen-doped carbon nanotube (nitrogen content 2.54 wt%) were put into a flask, and 12ml of acetonitrile was used as a solvent, and the flask was stirred and heated to 70 ℃ with a stirring rate of 900rpm, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 70 ℃ at 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 4.40% by GC detection.
Example 18
1.00g of diphenylmethane, 0.51g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotube (nitrogen content 2.54 wt%) were put into a flask, and 12ml of acetonitrile was used as a solvent, and stirred at 900rpm and heated to 70 ℃,0.5 ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and the reaction was started for 1 hour, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were charged into a flask, 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at 900rpm, and 1.5ml of tert-butyl hydroperoxide (70% aq. Soln.) was injected to start timing, after 1 hour of reaction, the catalyst and the reaction liquid were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at 900rpm, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, the reaction was started for 0.5h, and then the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 4.78% by GC detection.
Example 21
1.01g of diphenylmethane, 0.52g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotube (nitrogen content 2.54 wt%) were put into a flask, and 12ml of acetonitrile was used as a solvent, and the flask was stirred and heated to 70 ℃ with a stirring rate of 900rpm, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected, and after 3 hours of reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, and 3ml of tert-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, and after 5 hours of reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were charged in a flask, and 12ml of acetonitrile was used as a solvent, stirred and heated to 70 ℃ at a stirring rate of 900rpm, and 3ml of tert-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, and after 7 hours of the reaction, the catalyst and the reaction liquid were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone 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 content 2.54 wt%) were put into a flask, and stirred and heated to 70 ℃ at a stirring speed of 300rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 4.63% by GC detection.
Example 25
0.98g of diphenylmethane, 0.55g of chlorobenzene (internal standard) and 25mg of nitrogen-doped carbon nanotube (nitrogen content 2.54 wt%) were put into a flask, and stirred and heated to 70 ℃ at 600rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected thereto, and after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 5.67% by GC detection.
The in-situ nitrogen-doped carbon nanotubes of example 26 were prepared by the following steps (angelwave Chemie International Edition,2011,50 (17), 3978-3982):
FeMo/Al 2 O 3 Spreading the catalyst on a porcelain boat, placing in a tube furnace, continuously charging a mixture of hydrogen and nitrogen for 30min to activate the catalyst, and injecting 10mL of aniline into the tube furnace at a flow rate of 3mL/h under an ammonia atmosphere and at a tube cavity temperature of 180 ℃. Removing residual FeMo/Al by using concentrated hydrochloric acid after cooling 2 O 3 And (5) a catalyst to obtain the in-situ nitrogen-doped carbon nanotube. In the literature, the nitrogen content of the material is measured by X-ray photoelectron spectroscopy, and the N/C atomic ratio is 4.5 percent and the nitrogen content is 4.99 percent by weight; in order to reduce the error of the determination method, the invention uses an element analysis method to determine the nitrogen content of the material, and the nitrogen content of the in-situ nitrogen-doped carbon nano tube is 4.14wt%, which is equivalent to the nitrogen content in the example 7.
Example 26
0.99g of diphenylmethane, 0.53g of chlorobenzene (internal standard) and 25mg of in-situ nitrogen-doped carbon nanotube were put into a flask, stirred and heated to 70 ℃ at a stirring rate of 900rpm with 12ml of acetonitrile as a solvent, and 3ml of t-butyl hydroperoxide (70% aq. Soln.) was injected to start the reaction, after 1 hour of the reaction, the catalyst and the reaction solution were separated using a 0.2 μm filter to obtain a liquid-phase mixture after the reaction, and the yield of benzophenone was 4.76% by GC detection.
From the examples 1 and 2-26, it can be seen that the yield of benzophenone prepared by the nitrogen-doped carbon nanotube catalysis is obviously improved; it can be seen from examples 7 and 26 that the nitrogen-doped carbon nanotubes prepared by 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; as can be seen from examples 2-7, the catalytic yield is higher for a range of nitrogen contents (yield is reduced for too high and too low); as can be seen from examples 8, 16 and 17, the nitrogen-doped carbon nanotubes have higher catalytic yield within a certain range (the yield is reduced when the nitrogen-doped carbon nanotubes are too high or too low); temperature, solvent type, amount of oxidant used, reaction time, stirring rate, etc. all have an effect on catalytic yield.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing diphenyl ketone from diphenylmethane is characterized by comprising the following steps:
in a solvent system, oxidation reaction of diphenylmethane is carried out by taking peroxide as an oxidant and nitrogen-doped carbon nano tubes as a catalyst.
2. The process for preparing benzophenone from diphenylmethane according to claim 1, wherein: the nitrogen content of the nitrogen-doped carbon nano tube is 0.5 to 5wt percent.
3. The process for preparing benzophenone from diphenylmethane according to claim 1, wherein: the preparation method of the nitrogen-doped carbon nano tube comprises the following steps: under the protective atmosphere, the carbon nano tube reacts with mixed solution of pyridine and cyclohexane or pyridine at the temperature of 600-800 ℃ to obtain the nitrogen-doped carbon nano tube.
4. A process for preparing diphenyl ketone from diphenyl methane according to claim 3, characterized in that: 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 the pyridine is 0.05g:0.5-3ml;
the protective atmosphere is argon.
5. The process for preparing diphenyl ketone from diphenyl methane according to claim 1, characterized in that: the temperature of the oxidation reaction is 30-70 ℃.
6. The process for preparing diphenyl ketone from diphenyl methane according to claim 1, characterized in that: 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.
7. The process for preparing diphenyl ketone from diphenyl methane according to claim 1, characterized in that: the mass ratio of the nitrogen-doped carbon nano tube to the diphenylmethane is 0.01-0.05: 1.
8. the process for preparing benzophenone from diphenylmethane according to claim 1, wherein: the peroxide is tert-butyl hydroperoxide; the molar ratio of the peroxide to the diphenylmethane is 0.5-3: 1.
9. the process for preparing diphenyl ketone from diphenyl methane according to claim 1, characterized in that: the time of the oxidation reaction is 0.5-9 h.
10. Process for the preparation of benzophenone from diphenylmethane according to any one of claims 1 to 9, characterized in that: the oxidation reaction is carried out under the condition of stirring, and the stirring speed is 300-900 rpm.
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