CN112010730A - Green preparation method of diphenylmethane - Google Patents
Green preparation method of diphenylmethane Download PDFInfo
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- CN112010730A CN112010730A CN202010750582.0A CN202010750582A CN112010730A CN 112010730 A CN112010730 A CN 112010730A CN 202010750582 A CN202010750582 A CN 202010750582A CN 112010730 A CN112010730 A CN 112010730A
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- benzophenone
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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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012965 benzophenone Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000004817 gas chromatography Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000019717 geranium oil Nutrition 0.000 description 3
- 239000010648 geranium oil Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002699 waste material Substances 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
- 229920001661 Chitosan Polymers 0.000 description 1
- 235000005976 Citrus sinensis Nutrition 0.000 description 1
- 240000002319 Citrus sinensis Species 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930194936 Tylosin Natural products 0.000 description 1
- 239000004182 Tylosin Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- DERZBLKQOCDDDZ-JLHYYAGUSA-N cinnarizine Chemical compound C1CN(C(C=2C=CC=CC=2)C=2C=CC=CC=2)CCN1C\C=C\C1=CC=CC=C1 DERZBLKQOCDDDZ-JLHYYAGUSA-N 0.000 description 1
- 229960000876 cinnarizine Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229960000525 diphenhydramine hydrochloride Drugs 0.000 description 1
- -1 diphenyl halogenated methane Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- DWAFYCQODLXJNR-BNTLRKBRSA-L oxaliplatin Chemical compound O1C(=O)C(=O)O[Pt]11N[C@@H]2CCCC[C@H]2N1 DWAFYCQODLXJNR-BNTLRKBRSA-L 0.000 description 1
- 229960001756 oxaliplatin Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 description 1
- 229960004059 tylosin Drugs 0.000 description 1
- 235000019375 tylosin Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a green preparation method of diphenylmethane, which comprises the following steps: (1) adding benzophenone, an organic solvent and a catalyst into a hydrogenation reaction kettle in sequence, introducing hydrogen, stirring, performing a displacement reaction at the temperature of 0-180 ℃ and under the pressure of 0.1-10 MPa, and finishing the reaction when the hydrogenation reaction kettle is introduced with hydrogen until the hydrogen is not absorbed any more, (2) cooling the hydrogenation reaction kettle to room temperature, taking out a reaction solution, filtering out the catalyst, and recovering and reusing the catalyst; concentrating the filtrate at normal pressure for later use; recovering the organic solvent in the process of concentrating the filtrate at normal pressure, and recycling; (3) and (4) carrying out reduced pressure rectification on the concentrated filtrate to ensure that the gas chromatography normalized purity of the diphenylmethane is 99 percent, thus obtaining the product. The invention provides a catalytic hydrogenation synthesis process of diphenylmethane, which is simple in reaction process, pollution-free, green, environment-friendly and efficient.
Description
Technical Field
The invention relates to the field of chemical synthesis, and particularly relates to a green preparation method of diphenylmethane.
Background
Diphenylmethane, commonly known as artificial geranium oil, is a low-melting-point solid, has fragrance of geranium oil and sweet orange oil, and is an important spice, dye, pesticide and medical intermediate. The pharmaceutical industry is used for producing diphenhydramine hydrochloride; the derivative such as diphenyl halogenated methane can be used for synthesizing medicines such as tylosin, cinnarizine, oxaliplatin and the like. In the fragrance industry, diphenylmethane serves as a substitute for geranium oil and is suitable for formulating soap essences, perfumes and the like. The synergist or additive is commonly used as pesticide in fine chemistry industry, and can also be used for dye production.
The synthesis of diphenylmethane by the friedel-crafts alkylation of benzene is a widely used method, the alkylating agents are generally benzyl chloride and benzyl alcohol, the catalysts are generally catalysts including acid halides (lewis acid), protonic acid, acid oxide, alkyl aluminum and the like, and AlCl is commonly used in the acid halides3、ZnCl2And BF3And complexes thereof; the protonic acid is usually concentrated H2SO4HF acid, and the like.
The above catalysts have many disadvantages, AlCl3、ZnCl2When the selectivity of the acidic halide catalyst is low, a large amount of HCl gas is generated, the catalyst needs to be hydrolyzed to release heat when the product is separated, and a large amount of salt-containing waste liquid is generated, so that the equipment and the environment are polluted. Concentrated H2SO4Due to acidity and oxidizability, a large amount of byproducts are generated in the reaction process, the post-treatment process of the product is complex, and the concentrated H is2SO4Liquid acids such as HF and the like are severely corrosive and cause pollution to equipment and environment.
In addition, the diphenylmethane serving as a byproduct of the alkylation has higher reactivity than that of the benzene serving as a raw material, and a large excess of benzene with high toxicity is generally added for inhibiting the polyalkylation product, but even if the benzene is added, the selectivity of the product is not high, the yield of the product is only 60-70% generally, and a large amount of useless waste residues are generated.
There are also other methods:
patent CN104496739A reports a method for synthesizing diphenylmethane by using solid acid catalyst, and the reaction conditions require high temperature and high pressure.
Patent CN1631861A invented a ZnCl2clay-SA 0.1 catalytic synthesis of diphenyl methane. The yield is general, and the product is not easy to separate.
Patent CN102329191A discloses an immobilized aluminum chloride catalyst using chitosan as a carrier, which is used for catalyzing the reaction of benzene and benzyl chloride to synthesize diphenylmethane.
Patent CN103304366A discloses a method for synthesizing diphenylmethane by condensation reaction of benzene and formaldehyde as raw materials under the action of various solid acid catalysts. The raw materials used in the method are cheaper, but the disclosed preparation yield is very low, and the method has no industrial value.
Disclosure of Invention
In view of the above-mentioned drawbacks or deficiencies of the prior art, it would be desirable to provide a green process for the production of diphenylmethane.
According to the technical scheme provided by the embodiment of the application, the green preparation method of the diphenylmethane comprises the following steps:
(1) adding benzophenone, organic solvent and catalyst into a hydrogenation reaction kettle in turn,
the volume ratio of the organic solvent to the benzophenone is 1-20:1,
the mass ratio of the catalyst to the benzophenone is 0.3-30:100,
introducing hydrogen, stirring, performing displacement reaction at 0-180 deg.C and 0.1-10 MPa, stopping reaction when hydrogen is not absorbed,
the preparation reaction equation is as follows:
(2) cooling the hydrogenation reaction kettle to room temperature, taking out reaction liquid, filtering out the catalyst, and recovering and reusing the catalyst; concentrating the filtrate at normal pressure for later use; recovering the organic solvent in the process of concentrating the filtrate at normal pressure, and recycling;
(3) and (4) carrying out reduced pressure rectification on the concentrated filtrate to ensure that the gas chromatography normalized purity of the diphenylmethane is 99 percent, thus obtaining the product.
In the invention, the organic solvent is one of alcohol solvents, hydrocarbon solvents and ether solvents, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
In the invention, the organic solvent is a mixed solvent of any two of an alcohol solvent, a hydrocarbon solvent and an ether solvent, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
In the invention, the catalyst is one of palladium catalyst, nickel catalyst and platinum catalyst, and the mass ratio of the catalyst to the benzophenone is 1-10: 100.
In the invention, the catalyst is palladium carbon catalyst or Raney nickel catalyst.
In the invention, the reaction temperature of the hydrogenation reaction kettle is 20-120 ℃, and the reaction pressure is 0.2-4 MPa.
To sum up, the beneficial effect of this application: the invention provides a catalytic hydrogenation synthesis process of diphenylmethane, which is simple in reaction process, pollution-free, green, environment-friendly and efficient.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the invention are shown in the embodiments.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
A green preparation method of diphenylmethane comprises the following steps:
(1) adding benzophenone, organic solvent and catalyst into a hydrogenation reaction kettle in turn,
the volume ratio of the organic solvent to the benzophenone is 1-20:1,
the mass ratio of the catalyst to the benzophenone is 0.3-30:100,
introducing hydrogen, stirring, performing displacement reaction at 0-180 deg.C and 0.1-10 MPa, stopping reaction when hydrogen is not absorbed,
the preparation reaction equation is as follows:
(2) cooling the hydrogenation reaction kettle to room temperature, taking out reaction liquid, filtering out the catalyst, and recovering and reusing the catalyst; concentrating the filtrate at normal pressure for later use; recovering the organic solvent in the process of concentrating the filtrate at normal pressure, and recycling;
(3) and (4) carrying out reduced pressure rectification on the concentrated filtrate to ensure that the gas chromatography normalized purity of the diphenylmethane is 99 percent, thus obtaining the product.
The organic solvent is one of alcohol solvent, hydrocarbon solvent and ether solvent, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
The organic solvent is a mixed solvent of any two of alcohol solvents, hydrocarbon solvents and ether solvents, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
The catalyst is one of palladium catalyst, nickel catalyst and platinum catalyst, and the mass ratio of the catalyst to the benzophenone is 1-10: 100.
The catalyst is one of palladium carbon catalyst and Raney nickel catalyst.
The reaction temperature of the hydrogenation reaction kettle is 20-120 ℃, and the reaction pressure is 0.2-4 MPa.
Example 1:
91g (0.5mol) of benzophenone and 350g of petroleum ether (90-120 ℃) are added into a 1L hydrogenation kettle, 1g of 5% Pd/C is added, after a device is arranged and hydrogen is replaced, hydrogen is introduced to 2MPa, heating is started, the temperature is controlled to be 60-70 ℃, and hydrogen is introduced to react for about 6 hours under the pressure of 1-2 MPa. After the hydrogen absorption is finished, cooling to room temperature, filtering to remove the catalyst, carrying out rotary evaporation on the filtrate to remove the solvent, carrying out vacuum rectification on the residual liquid, collecting 80g of 108-value 112 ℃/1000KPa distillate, wherein the yield is 95 percent, and the purity is 99.5 percent through gas chromatography detection. The recovered solvent and the catalyst can be used repeatedly, and the activity of the catalyst is not obviously reduced after the catalyst is used repeatedly for more than 10 times.
Example 2:
adding 91g (0.5mol) of benzophenone, 380g of toluene and 0.8g of 10% Pd/C into a 1L hydrogenation kettle, filling hydrogen to 1MPa after a device is arranged and a hydrogen gas is replaced, starting heating, controlling the temperature to be 60-70 ℃, and filling hydrogen under the pressure of 0.5-1 MPa for reaction for about 5 hours. And finishing hydrogen absorption. The product was worked up in the same manner as in example 1 to give 81g of a product with a yield of 96.4% and a purity of 99.6% by gas chromatography.
Example 3:
91g (0.5mol) of benzophenone, 150g of petroleum ether (90-120 ℃) in a 1L hydrogenation kettle, 200g of absolute ethyl alcohol and 1g of 5% Pd/C are added, after the hydrogen replacement of the device is finished, hydrogen is introduced to 2MPa, heating is started, the temperature is controlled to be 60-70 ℃, and the hydrogen is introduced to react for about 6 hours under the pressure of 1-2 MPa. After the hydrogen absorption was completed, the product was worked up in the same manner as in example 1 to give 80g of a product in a yield of 95% and a purity of 99.5% by gas chromatography.
Example 4:
adding 91g (0.5mol) of benzophenone, 400g of methanol and 5g R-Ni into a 1L hydrogenation kettle, filling hydrogen to 3MPa after a device is arranged and hydrogen is replaced, starting heating, controlling the temperature to be 70-80 ℃ and filling hydrogen at the pressure of 2.5-3MPa for reaction for about 7 hours. And finishing hydrogen absorption. The product was worked up in the same manner as in example 1 to give 81g of a product with a yield of 96.4% and a purity of 99.6% by gas chromatography. The recovered solvent (after dehydration) and the catalyst can be used repeatedly, and the activity of the catalyst is not obviously reduced after the catalyst is used repeatedly for more than 8 times.
Example 5:
91g (0.5mol) of benzophenone, 380g of THF and 5g R-Ni are added into a 1L hydrogenation kettle, after a device is arranged and hydrogen is replaced, hydrogen is introduced to 2.5MPa, heating is started, the temperature is controlled at 70-80 ℃, and hydrogen is introduced to react for about 7 hours under the pressure of 2.0-2.5 MPa. And finishing hydrogen absorption. The product was worked up in the same manner as in example 1 to give 81g of a product with a yield of 96.4% and a purity of 99.6% by gas chromatography.
Pd/C is a palladium-carbon catalyst and plays a role of a catalyst, and the specific process is catalytic hydrogenation.
THF is tetrahydrofuran.
R-Ni is a Raney nickel catalyst and plays a role of a catalyst, and the specific process is catalytic hydrogenation.
Detection conditions of the gas phase:
sample inlet temperature: 280 ℃, split ratio: 100:1, column box: initial 70 ℃ hold 2min, 20 ℃ min up to 280 ℃, hold 12.5min, detector temperature: at 300 ℃.
The foregoing description is only exemplary of the preferred embodiments of the application and is provided for the purpose of illustrating the general principles of the technology and the like. Meanwhile, the scope of the invention according to the present application is not limited to the technical solutions in which the above-described technical features are combined in a specific manner, and also covers other technical solutions in which the above-described technical features or their equivalent are combined arbitrarily without departing from the inventive concept described above. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (6)
1. A green preparation method of diphenylmethane is characterized by comprising the following steps: the method comprises the following steps:
(1) adding benzophenone, organic solvent and catalyst into a hydrogenation reaction kettle in turn,
the volume ratio of the organic solvent to the benzophenone is 1-20:1,
the mass ratio of the catalyst to the benzophenone is 0.3-30:100,
introducing hydrogen, stirring, performing displacement reaction at 0-180 deg.C and 0.1-10 MPa, stopping reaction when hydrogen is not absorbed,
the preparation reaction equation is as follows:
(2) cooling the hydrogenation reaction kettle to room temperature, taking out reaction liquid, filtering out the catalyst, and recovering and reusing the catalyst; concentrating the filtrate at normal pressure for later use; recovering the organic solvent in the process of concentrating the filtrate at normal pressure, and recycling;
(3) and (4) carrying out reduced pressure rectification on the concentrated filtrate to ensure that the gas chromatography normalized purity of the diphenylmethane is 99 percent, thus obtaining the product.
2. The green process for preparing diphenylmethane according to claim 1, wherein: the organic solvent is one of alcohol solvent, hydrocarbon solvent and ether solvent, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
3. The green process for preparing diphenylmethane according to claim 1, wherein: the organic solvent is a mixed solvent of any two of alcohol solvents, hydrocarbon solvents and ether solvents, the organic solvent comprises methanol, ethanol, isopropanol, petroleum ether, cyclohexane, benzene, toluene and tetrahydrofuran, and the volume ratio of the organic solvent to the benzophenone is 2-8: 1.
4. The green process for preparing diphenylmethane according to claim 1, wherein: the catalyst is one of palladium catalyst, nickel catalyst and platinum catalyst, and the mass ratio of the catalyst to the benzophenone is 1-10: 100.
5. The green process for preparing diphenylmethane according to claim 4, wherein: the catalyst is palladium carbon catalyst or Raney nickel catalyst.
6. The green process for preparing diphenylmethane according to claim 1, wherein: the reaction temperature of the hydrogenation reaction kettle is 20-120 ℃, and the reaction pressure is 0.2-4 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11338271B2 (en) * | 2018-02-21 | 2022-05-24 | Dexerials Corporation | Porous carbon material, method for producing same, and catalyst for synthesis reaction |
| CN117486802A (en) * | 2024-01-03 | 2024-02-02 | 启农生物科技(北京)有限公司 | Method for preparing imidazole ethanol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050165255A1 (en) * | 2002-05-30 | 2005-07-28 | Konica Minolta Chemical Co., Ltd. | Method for producing 2-benzylaniline |
| CN102241566A (en) * | 2011-05-09 | 2011-11-16 | 中山奕安泰医药科技有限公司 | Method for preparing diphenyl carbinol and derivatives thereof |
| CN105461580A (en) * | 2015-11-12 | 2016-04-06 | 上虞颖泰精细化工有限公司 | Synthesis method of metolachlor |
-
2020
- 2020-07-30 CN CN202010750582.0A patent/CN112010730A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050165255A1 (en) * | 2002-05-30 | 2005-07-28 | Konica Minolta Chemical Co., Ltd. | Method for producing 2-benzylaniline |
| CN102241566A (en) * | 2011-05-09 | 2011-11-16 | 中山奕安泰医药科技有限公司 | Method for preparing diphenyl carbinol and derivatives thereof |
| CN105461580A (en) * | 2015-11-12 | 2016-04-06 | 上虞颖泰精细化工有限公司 | Synthesis method of metolachlor |
Non-Patent Citations (2)
| Title |
|---|
| TOMOHIRO HATTORI, ET AL.: "Systematic evaluation of the palladium-catalyzed hydrogenation under flow conditions", 《TETRAHEDRON》 * |
| 沖本光宏, 千葉俊郎, 高田善之: "Raneyニッケルを用いた硫酸水溶液中ての還元", 《日本化学会志》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11338271B2 (en) * | 2018-02-21 | 2022-05-24 | Dexerials Corporation | Porous carbon material, method for producing same, and catalyst for synthesis reaction |
| CN117486802A (en) * | 2024-01-03 | 2024-02-02 | 启农生物科技(北京)有限公司 | Method for preparing imidazole ethanol |
| CN117486802B (en) * | 2024-01-03 | 2024-04-19 | 启农生物科技(北京)有限公司 | Method for preparing imidazole ethanol |
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