CN113956143A - Preparation method of m-trifluoromethyl acetophenone - Google Patents
Preparation method of m-trifluoromethyl acetophenone Download PDFInfo
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- CN113956143A CN113956143A CN202111345150.2A CN202111345150A CN113956143A CN 113956143 A CN113956143 A CN 113956143A CN 202111345150 A CN202111345150 A CN 202111345150A CN 113956143 A CN113956143 A CN 113956143A
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- Prior art keywords
- trifluoromethylacetophenone
- trifluoromethylbenzene
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- trifluoromethyl
- trifluoromethyl acetophenone
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- ABXGMGUHGLQMAW-UHFFFAOYSA-N 1-[3-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=CC(C(F)(F)F)=C1 ABXGMGUHGLQMAW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 54
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- MLIYIKGLAHXJLX-UHFFFAOYSA-N 1,2,3,4-tetrachloro-5,6-dihydrobenzo[b][1]benzoxepine Chemical compound ClC1=C(C(=C(C2=C1OC1=C(C=CC=C1)CC2)Cl)Cl)Cl MLIYIKGLAHXJLX-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LBWMQVOHFPLVBY-UHFFFAOYSA-N 3,3,3-trifluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)CC(=O)C1=CC=CC=C1 LBWMQVOHFPLVBY-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 229930182692 Strobilurin Natural products 0.000 description 1
- 239000005857 Trifloxystrobin Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of m-trifluoromethyl acetophenone, and relates to the technical field of chemical synthesis; according to the method, trifluoromethylbenzene and acetic acid are used as raw materials in a solvent, condensation reaction is carried out under the action of a catalyst, the solvent is removed by distillation, and the m-trifluoromethylacetophenone is obtained, wherein the content is more than or equal to 99.0%, and the total yield is more than or equal to 95.0% in terms of the trifluoromethylbenzene; the method has the advantages of simple process flow, safe and convenient operation, higher product quality and yield of the m-trifluoromethyl acetophenone, lower consumption, low production cost, less three wastes, and reduction of environmental protection pressure, meets the requirement of clean production, and is favorable for large-scale industrial production.
Description
Technical Field
The invention discloses a method, relates to the technical field of chemical synthesis, and particularly relates to a preparation method of m-trifluoromethyl acetophenone.
Background
The m-trifluoromethyl acetophenone is an important organic synthesis intermediate, and is mainly used in the fields of pesticides, medicines, dyes, liquid crystal materials and the like. However, in the prior art for preparing the m-trifluoromethyl acetophenone, some methods have high price of starting materials, difficult sources, low yield and difficult industrialization; cadmium chloride is used in some methods, so that the treatment difficulty of waste water is increased; some methods use diazomethane, which is explosive and highly toxic; some industrialized methods have low yield, high cost, large amount of three wastes and large safety risk in raw materials or production processes.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of m-trifluoromethyl acetophenone, which has the characteristics of mild reaction process, simple process flow, safe and convenient operation, good product quality, high yield, low production cost, less three wastes, capability of meeting the requirement of clean production and suitability for large-scale industrial production.
The specific scheme provided by the invention is as follows:
a process for preparing m-trifluoromethyl acetophenone includes condensation reaction of trifluoromethyl benzene and acetic acid in solvent under the action of catalyst, washing with water, laying aside for layering,
and (3) obtaining an oil phase, and distilling the oil phase to remove the solvent to obtain the m-trifluoromethyl acetophenone.
Preferably, in the preparation method of m-trifluoromethylacetophenone, the catalyst is selected from one or two of 4-dimethylaminopyridine, tetrabutyl ammonium hydroxide, dicyclohexylcarbodiimide, polyethylene glycol with molecular weight of 200-.
Preferably, in the preparation method of the m-trifluoromethyl acetophenone, the mass ratio of the catalyst to the trifluoromethyl benzene is 0.0005-0.1: 1.
Preferably, in the preparation method of m-trifluoromethylacetophenone, the solvent is one of butanone, 3-pentanone, toluene, xylene, chlorobenzene, chlorotoluene, petroleum ether, n-hexane, cyclohexane, petroleum ether, ethyl acetate, diisopropyl ether, ethyl n-propyl ether, diisobutyl ether, tetrachloroethylene, diphenyl ether, isooctane, chloroform, dichloroethane, trichloroethane and tetrachloroethane.
Preferably, in the preparation method of the m-trifluoromethyl acetophenone, the mass ratio of the solvent to the trifluoromethyl benzene is 0.5-10: 1.
Preferably, in the preparation method of the m-trifluoromethyl acetophenone, the molar ratio of the trifluoromethyl benzene to the acetic acid is 1: 1.01-1.2.
Preferably, the mass ratio of the washing water to the trifluoromethyl benzene in the preparation method of the m-trifluoromethyl acetophenone is 0.1-0.5: 1.
Preferably, in the preparation method of the m-trifluoromethyl acetophenone, the condensation reaction is carried out at the temperature of 40-150 ℃.
The invention also provides the m-trifluoromethyl acetophenone which is obtained by the preparation method of the m-trifluoromethyl acetophenone.
The invention also provides application of the m-trifluoromethyl acetophenone.
The invention has the advantages that:
the invention provides a preparation method of m-trifluoromethyl acetophenone, which adopts a route of synthesizing the m-trifluoromethyl acetophenone by using trifluoromethyl benzene and acetic acid, has mild reaction process, simple process flow, small safety risk, more convenient operation, easy realization of automatic control and suitability for large-scale industrial production;
and no dangerous solid waste and dangerous waste liquid exist, so that pollutants are reduced, the environmental protection pressure is reduced, and the process is clean in production;
the method improves the content and yield of the m-trifluoromethyl acetophenone, reduces the production cost, and has the content of the m-trifluoromethyl acetophenone more than or equal to 99.0 percent and the total yield more than or equal to 95.0 percent based on the trifluoromethyl benzene.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
The invention provides a preparation method of m-trifluoromethyl acetophenone, which comprises the steps of carrying out condensation reaction on trifluoromethyl benzene and acetic acid in a solvent as raw materials under the action of a catalyst, adding water for washing after the reaction is finished, standing for layering,
and (3) obtaining an oil phase, and distilling the oil phase to remove the solvent to obtain the m-trifluoromethyl acetophenone.
The reaction principle of the invention can be referred to the following reaction formula:
based on the technical solution of the present invention, in some embodiments of the present invention, preferably, in the preparation method of m-trifluoromethylacetophenone, the catalyst may be one or two of 4-dimethylaminopyridine, tetrabutylammonium hydroxide, dicyclohexylcarbodiimide, polyethylene glycol with a molecular weight of 200-.
In addition to the above examples, or in other examples, preferably, the mass ratio of the catalyst to the trifluoromethylbenzene in the preparation method of the m-trifluoromethylacetophenone may be 0.0005 to 0.1: 1.
In addition to the above embodiments, or in another embodiment, preferably, in the method for preparing m-trifluoromethyl acetophenone, the solvent may be one of butanone, 3-pentanone, toluene, xylene, chlorobenzene, chlorotoluene, petroleum ether, n-hexane, cyclohexane, petroleum ether, ethyl acetate, diisopropyl ether, ethyl n-propyl ether, diisobutyl ether, tetrachloroethylene, diphenyl ether, isooctane, chloroform, dichloroethane, trichloroethane, and tetrachloroethane. Further preferably, in the preparation method of m-trifluoromethylacetophenone, the mass ratio of the solvent to the trifluoromethylbenzene is 0.5-10: 1.
And on the basis of the above embodiment, or preferably in another embodiment, in the preparation method of m-trifluoromethylacetophenone, the molar ratio of the trifluoromethylbenzene to the acetic acid is 1: 1.01-1.2.
And on the basis of the above embodiment, or preferably in another embodiment, the mass ratio of the washing water to the trifluoromethylbenzene in the preparation method of the m-trifluoromethylacetophenone is 0.1-0.5: 1.
On the basis of the above embodiment, or preferably in another embodiment, in the preparation method of m-trifluoromethylacetophenone, the condensation reaction is carried out at the temperature of 40-150 ℃, under the normal pressure condition or under the pressurization condition (0-1.6 MPa of nitrogen), and for 1-10 h.
In conclusion, the content of the m-trifluoromethyl acetophenone obtained in the embodiment is more than or equal to 99.0 percent, and the total yield is more than or equal to 95.0 percent based on the trifluoromethyl benzene.
To further specifically illustrate the above embodiments, the embodiments can be applied to industrial production, and only some of the embodiments are representative of the embodiments to implement the process in the experiment or production, and the embodiments are not limited to properly adjust the reaction conditions, the amount of raw materials, the equipment used, and the like in the actual production within the framework of the technical solution of the present invention.
Example 1:
296g of toluene, 147.6g of trifluoromethylbenzene, 63.6g of acetic acid and 1.5g of sodium methoxide are put into a 1000ml reaction bottle, stirred and heated to 40-70 ℃ for reaction for 4 hours, cooled to normal temperature, washed by 20g of water, kept stand for layering, a water phase is separated, an oil phase is subjected to reduced pressure distillation to remove the toluene, the weight of the m-trifluoromethylacetophenone is 181.1kg, the content is 99.2 percent, and the yield is 95.5 percent calculated by the trifluoromethylbenzene.
Example 2:
in a 5000ml reaction bottle, 1180g of chlorobenzene, 782g of trifluoromethylbenzene, 340g of acetic acid, 3.0g of 4-dimethylaminopyridine and 1.2g of tetrabutylammonium chloride are added, the mixture is stirred and heated to 80-100 ℃ for reaction for 6 hours, the temperature is reduced to normal temperature, 80g of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase, chlorobenzene is removed, the weight of the m-trifluoromethylacetophenone is 964kg, the content of the m-trifluoromethylacetophenone is 99.3%, and the yield is 96.0% in terms of the trifluoromethylbenzene.
Example 3:
3000kg of ethyl acetate, 400kg of trifluoromethylbenzene, 173kg of acetic acid, 18-crown-64 kg and 1.5kg of cyclodextrin are put into a 5000l glass lining reaction kettle, stirred and heated to 65-75 ℃ for reaction for 7 hours, cooled to normal temperature, washed by 100kg of water, kept stand for layering, separated out a water phase, and subjected to reduced pressure distillation of an oil phase to remove the ethyl acetate, wherein the weight of the m-trifluoromethylacetophenone is 490kg, the content of the m-trifluoromethylacetophenone is 99.5 percent, and the yield is 95.6 percent calculated by the trifluoromethylbenzene.
Example 4:
4000kg of ethyl n-propyl ether, 1000kg of trifluoromethyl benzene, 472kg of acetic acid, 30kg of tetrabutylammonium bromide, 6kg of sodium tert-butoxide and 0.5-0.6MPa of nitrogen pressurization are added into a 8000l stainless steel reaction kettle, stirred and heated to 65-75 ℃ for reaction for 9 hours, the temperature is reduced to normal temperature, 300kg of water is added for washing, standing and layering are carried out, a water phase is separated, the oil phase is subjected to reduced pressure distillation to remove the ethyl n-propyl ether, the weight of the m-trifluoromethyl acetophenone is 1232kg, the content is 99.6 percent, and the yield is 96.3 percent calculated by the trifluoromethyl benzene.
Example 5:
2000kg of dichloroethane, 2000kg of trifluoromethylbenzene, 986kg of acetic acid, 4kg of dodecyl trimethyl ammonium chloride, 1kg of sodium amide and 0.6-1.0MPa of nitrogen pressurization are put into a 6300l stainless steel reaction kettle, stirred and heated to 85-100 ℃ for reaction for 4 hours, the temperature is reduced to normal temperature, 400kg of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase, dichloroethane is removed, the weight of the m-trifluoromethylacetophenone is 2457kg, the content of the m-trifluoromethylacetophenone is 99.4%, and the yield is 95.8% in terms of the trifluoromethylbenzene.
Example 6:
1500kg of tetrachloroethane, 3000kg of trifluoromethylbenzene, 1281kg of acetic acid, 2kg of triphenylphosphine, 4kg of hexamethylphosphoric triamide and 1.0-1.6MPa of nitrogen are put into a 8000l stainless steel reaction kettle, stirred and heated to 100 ℃ and 150 ℃ for reaction for 3 hours, the temperature is reduced to normal temperature, 500kg of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase to remove tetrachloroethane, the weight of the m-trifluoromethylacetophenone is 3509kg, the content is 99.2 percent, and the yield is 95.5 percent calculated by the trifluoromethylbenzene.
Example 7:
1500kg of butanone, 3000kg of trifluoromethylbenzene, 1293kg of acetic acid, 3kg of tetrabutyl ammonium hydroxide, 18-crown-63 kg of butanone and 1.0-1.6MPa of nitrogen are put into a 8000l stainless steel reaction kettle, stirred and heated to 70-85 ℃ for reaction for 3 hours, the temperature is reduced to normal temperature, 500kg of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase, butanone is removed, the weight of the m-trifluoromethylacetophenone is 3666kg, the content of the m-trifluoromethylacetophenone is 99.3%, and the yield is 95.2% calculated by the trifluoromethylbenzene.
Example 8:
1500kg of dimethylbenzene, 3000kg of trifluoromethylbenzene, 1416kg of acetic acid, 1.2kg of tetrabutyl ammonium chloride, 3kg of sodium ethoxide and 1.0-1.6MPa of nitrogen are put into a 8000l stainless steel reaction kettle, stirred and heated to 145 ℃ for reaction for 3 hours, the temperature is reduced to normal temperature, 500kg of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase, the dimethylbenzene is removed, the weight of the m-trifluoromethylacetophenone is 3674kg, the content is 99.3 percent, and the yield is 95.4 percent calculated by the trifluoromethylbenzene.
Example 9:
1500kg of cyclohexane, 3000kg of trifluoromethylbenzene, 1355kg of acetic acid, 6004.2 kg of polyethylene glycol, 1.5kg of sodium amide and 1.0-1.6MPa of nitrogen are added into a 8000l stainless steel reaction kettle, stirred and heated to 70-85 ℃ for reaction for 5 hours, the temperature is reduced to normal temperature, 500kg of water is added for washing, standing and layering are carried out, a water phase is separated, reduced pressure distillation is carried out on an oil phase, cyclohexane is removed, the weight of the m-trifluoromethylacetophenone is 3697kg, the content of the m-trifluoromethylacetophenone is 99.0%, and the yield is 95.7% calculated by the trifluoromethylbenzene.
Example 10:
1500kg of trichloroethane, 3000kg of trifluoromethylbenzene, 1330kg of acetic acid, 2.4kg of tetradecyltrimethylammonium chloride, 3kg of potassium tert-butoxide and 1.0-1.6MPa of nitrogen are added into a 8000l stainless steel reaction kettle, stirred and heated to 110 ℃ and 120 ℃ for reaction for 4 hours, the temperature is reduced to normal temperature, 500kg of water is added for washing, the mixture is kept stand for layering, a water phase is separated, reduced pressure distillation is carried out on an oil phase to remove the trichloroethane, the weight of the m-trifluoromethylacetophenone is 3655kg, the content is 99.5 percent, and the yield is 95.1 percent calculated by the trifluoromethylbenzene.
The invention also provides the m-trifluoromethyl acetophenone which is obtained by the preparation method of the m-trifluoromethyl acetophenone.
The invention also provides application of the m-trifluoromethyl acetophenone. The intermediate trifluoromethyl acetophenone is used as an organic synthesis intermediate, and can be used in the fields of pesticides, medicines, dyes, liquid crystal materials and the like. And can be used for synthesizing pesticides such as strobilurin fungicide trifloxystrobin and the like.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A process for preparing m-trifluoromethyl acetophenone includes condensation reaction of trifluoromethyl benzene and acetic acid in solvent under the action of catalyst, washing with water, laying aside for layering,
and (3) obtaining an oil phase, and distilling the oil phase to remove the solvent to obtain the m-trifluoromethyl acetophenone.
2. The method for preparing m-trifluoromethylacetophenone of claim 1, wherein the catalyst is one or two of 4-dimethylaminopyridine, tetrabutyl ammonium hydroxide, dicyclohexylcarbodiimide, polyethylene glycol with molecular weight of 200-.
3. The process for preparing m-trifluoromethylacetophenone according to claim 1 or 2, wherein the mass ratio of the catalyst to the trifluoromethylbenzene is 0.0005 to 0.1: 1.
4. The method for preparing m-trifluoromethylacetophenone according to claim 1, wherein the solvent is selected from one of butanone, 3-pentanone, toluene, xylene, chlorobenzene, chlorotoluene, petroleum ether, n-hexane, cyclohexane, petroleum ether, ethyl acetate, diisopropyl ether, ethyl n-propyl ether, diisobutyl ether, tetrachloroethylene, diphenyl ether, isooctane, chloroform, dichloroethane, trichloroethane and tetrachloroethane.
5. The method for preparing m-trifluoromethylacetophenone according to claim 1 or 4, characterized in that the mass ratio of the solvent to the trifluoromethylbenzene is 0.5-10: 1.
6. The method for preparing m-trifluoromethylacetophenone according to claim 1, wherein the molar ratio of the trifluoromethylbenzene to the acetic acid is 1: 1.01-1.2.
7. The process for preparing m-trifluoromethylacetophenone according to claim 1, wherein the mass ratio of the washing water to the trifluoromethylbenzene is 0.1-0.5: 1.
8. The process for preparing m-trifluoromethylacetophenone according to claim 1, wherein the condensation reaction is carried out at a temperature of 40 to 150 ℃.
9. A m-trifluoromethyl acetophenone, characterized in that it is obtained by the process for the preparation of a m-trifluoromethyl acetophenone according to any one of claims 1 to 8.
10. The use of a meta-trifluoromethylacetophenone according to claim 9.
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