CN112979443A - Continuous preparation method of trifluoromethyl butenone derivative - Google Patents
Continuous preparation method of trifluoromethyl butenone derivative Download PDFInfo
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- CN112979443A CN112979443A CN201911282778.5A CN201911282778A CN112979443A CN 112979443 A CN112979443 A CN 112979443A CN 201911282778 A CN201911282778 A CN 201911282778A CN 112979443 A CN112979443 A CN 112979443A
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- trifluoromethyl
- butenone
- trifluoromethylbutenone
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- WRYDZANLTJJLDW-UHFFFAOYSA-N 5,5,5-trifluoropent-1-en-3-one Chemical class FC(F)(F)CC(=O)C=C WRYDZANLTJJLDW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 18
- -1 trifluoroacetyl halide Chemical class 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical group FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010924 continuous production Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000792 Monel Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- IOOGIWIGKUAFIY-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethenoxy)ethene Chemical compound CCOC=COC=COCC IOOGIWIGKUAFIY-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- APXPUJWNYZULFP-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-en-1-one Chemical class FC(F)(F)C=C=O APXPUJWNYZULFP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- UBMYYGXGMPGCBO-UHFFFAOYSA-N cyclopenten-1-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CCCC1 UBMYYGXGMPGCBO-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- ZKRGOQFKLWMHAX-UHFFFAOYSA-N 1,1,1-trifluorohex-3-en-2-one Chemical class CCC=CC(=O)C(F)(F)F ZKRGOQFKLWMHAX-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LUDJENUUFWPHPJ-UHFFFAOYSA-N trimethyl-(3-methyl-1-trimethylsilyloxybut-1-enoxy)silane Chemical compound CC(C)C=C(O[Si](C)(C)C)O[Si](C)(C)C LUDJENUUFWPHPJ-UHFFFAOYSA-N 0.000 description 3
- ZKJNETINGMOHJG-GGWOSOGESA-N (e)-1-[(e)-prop-1-enoxy]prop-1-ene Chemical compound C\C=C\O\C=C\C ZKJNETINGMOHJG-GGWOSOGESA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- LTODOXSVDSLFCZ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyprop-1-enoxy)prop-1-ene Chemical compound COC(=COC=C(OC)C)C LTODOXSVDSLFCZ-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MVUMJYQUKKUOHO-AATRIKPKSA-N ethyl (e)-3-(dimethylamino)prop-2-enoate Chemical compound CCOC(=O)\C=C\N(C)C MVUMJYQUKKUOHO-AATRIKPKSA-N 0.000 description 1
- JXBLPDIZGMZWNB-UHFFFAOYSA-N ethyl 2-(dimethylaminomethylidene)-4,4,4-trifluoro-3-oxobutanoate Chemical compound CCOC(=O)C(=CN(C)C)C(=O)C(F)(F)F JXBLPDIZGMZWNB-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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 continuous preparation method of trifluoromethyl butenone derivatives, which comprises the following steps of reacting a raw material 1 shown in a structure (I) in the following reaction formula with trifluoroacetyl halide serving as a raw material 2 in a microchannel reactor to prepare the trifluoromethyl butenone derivatives shown in a structure (II):
wherein R is an electron donating group and can be conjugated with an olefin double bond; r1、R2Independently selected from hydrogen, C1-C20 alkyl, aryl or substituted aryl or silyl; x is halogen selected from fluorine, chlorine, bromine or iodine. The method has the advantages of good process universality, good atom economy, high yield, few byproducts, high product purity and the like.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for continuously preparing trifluoromethyl butenone derivatives in a microchannel reactor.
Background
The trifluoromethyl butenone derivative has more active reaction centers and is widely applied to preparing various fluorine-containing heterocyclic compounds. The trifluoromethyl butenyl ketone derivative has various different structures according to different substituents, and during synthesis, the trifluoromethyl butenyl ketone derivative with different structures can only adopt a specific reaction system and replace a reaction substrate, so that the reaction can not be carried out possibly. The prior art has also reported the synthesis of only individual compounds:
the patent US2011015406A and the literature "Synthesis of 1-methyl-3-trifluoromethyl-1H-pyrazole-4-formyl chloride" (pesticide, Vol. 51, No. 8, 570-572) disclose the preparation of trifluoromethyl butenone derivatives by using 3-dimethylamino ethyl acrylate and trifluoroacetyl chloride as raw materials and reacting under the catalysis of organic base, but the reaction yield is only 80.1%, and three wastes are generated.
Chem.1995,60,3523; fluorine chem.2005,126, 543; synthesis2001,431 et al disclose the synthesis of ethoxyvinyltrifluoromethyl ketone by using trifluoroacetyl chloride, but the yield of the method is 80-90%, and the reaction requires the use of a basic catalyst, thereby generating three wastes.
The japanese mitsui chemistry discloses the synthesis of trifluoromethylbutenone derivatives using phosgene as the acylating agent:
however, the phosgene adopted in the method is a highly toxic gas, and a large amount of nitrogen is needed to dilute the phosgene after the reaction is finished, so that the cost is high, and the environmental hazard is large.
The method can only prepare one trifluoromethyl butenone derivative, and the trifluoromethyl butenone derivative is changed into other substrates, so that the reaction adaptability is poor, the reaction is almost not reacted, different bases are used for catalysis preparation, and a large amount of three wastes are generated.
Disclosure of Invention
In order to solve the technical problems, the invention provides the continuous preparation method of the trifluoromethyl butenone derivative, which has the advantages of good process universality, high yield, less byproducts and environmental friendliness.
The purpose of the invention is realized by the following technical scheme:
a continuous preparation method of trifluoromethyl butenone derivatives adopts a raw material 1 shown in a structure (I) in the following reaction formula and trifluoroacetyl halide used as a raw material 2 to react in a microchannel reactor to prepare the trifluoromethyl butenone derivatives shown in a structure (II):
wherein R is an electron donating group and can be conjugated with an olefin double bond; r1、R2Independently selected from hydrogen, C1-C20 alkyl, aryl or substituted aryl or silyl; x is halogen selected from fluorine, chlorine, bromine or iodine. Preferably, R1、R2Independently selected from hydrogen, C1-C8 alkyl; x is chlorine or fluorine。
According to the above continuous production method of the trifluoromethylbutenone derivative, preferably, R is selected from any one of the following structures:
-O-Q1-S-Q2
wherein Q1, Q2, Q3 and Q4 are independently selected from-CnH2n+2，-CnH2n，-CnH2n-2-Ar, -COR ', -COOR ', wherein n is greater than or equal to 12 and is greater than or equal to 2, and R ' is alkyl with the carbon number less than 12.
According to the above-mentioned continuous production method of a trifluoromethylbutenone derivative, preferably, the continuous production method comprises the steps of:
A1. the raw material 1 and the raw material 2 enter a reaction module of a microchannel reactor, the reaction temperature is-20-30 ℃, the reaction pressure is 0-1.0 Mpa, the molar ratio of the raw material 1 to the raw material 2 is 1: 1-1.5, and the flow rate of the raw material 1 is 1-50 g/min;
A2. and collecting the reaction liquid at the outlet of the reaction module to obtain a liquid part and a gas part, heating the liquid part to remove hydrogen halide in the liquid part to obtain trifluoromethyl butenone derivatives, and absorbing the gas part by water to obtain an acidic aqueous solution.
According to the above-mentioned continuous production method of the trifluoromethylbutenyl ketone derivative, optionally, the raw material 1 is selected from the group consisting of ethoxy vinyl ether, 1-methoxypropenyl ether, 2-methoxypropenyl ether and ethyl 3- (dimethylamino) acrylate.
According to the above-mentioned continuous preparation method of trifluoromethyl butenone derivatives, preferably, the heating temperature of the liquid part in the step A2 is20 ℃ to 100 ℃, so as to obtain trifluoromethyl butenone derivatives with purity of more than 99%. Preferably, the liquid portion is heated in step A2 at a temperature of 60 ℃ to 90 ℃.
According to the continuous preparation method of the trifluoromethyl ketene derivative, preferably, the molar ratio of the raw material 1 to the raw material 2 is 1: 1-1.2, the flow rate of the raw material 1 is 20-40 g/min, the reaction pressure is 0-0.5 MPa, and the reaction temperature is-10-20 ℃.
According to the above continuous preparation method of trifluoromethyl ketene derivatives, optionally, the raw material 1 is dissolved in a solvent and then enters the reaction module, wherein the solvent is at least one selected from toluene, dichloromethane, acetonitrile and dichloroethane.
According to the continuous preparation method of the trifluoromethyl ketene derivatives, preferably, the mass transfer coefficient of the microchannel reactor is 1-30 Ka, and the heat exchange capacity is 1700Kw/m2K or more.
According to the above continuous preparation method of the trifluoromethyl ketene derivative, preferably, the material of the reaction module is selected from silicon carbide, hac alloy or monel alloy.
According to the above continuous preparation method of the trifluoromethyl ketene butyrate derivative, preferably, the microchannel structure in the reaction module comprises a straight-flow channel structure and an enhanced mixed channel structure, the straight-flow channel structure is a tubular structure, the enhanced mixed channel structure is a T-shaped structure, a spherical structure, a drop-shaped structure or a heart-shaped structure, and the equivalent diameter of the enhanced mixed channel is 0.5mm to 10 mm. Preferably, the equivalent diameter of the reinforced hybrid type channel is 1mm to 6 mm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the microchannel reactor to continuously prepare the trifluoromethyl ketene derivatives, has good universality on raw materials with different structures under the same process parameters, and can obtain high conversion rate and high yield on different substrates.
(2) According to the continuous preparation process, the conversion rate of raw materials in a single reaction is more than 95%, the conversion rate of multiple cycles reaches 100%, and the purity of the prepared product is more than or equal to 99.0%.
(3) The continuous preparation process has the advantages of good atom economy, high yield and less byproducts, and simultaneously, alkali liquor is not required to be adopted in the reaction, thereby avoiding the defect of large three wastes in the traditional intermittent process.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The embodiment of the invention adopts a spherical microchannel reaction module, the equivalent diameter of the channel is 5mm, the material of the reaction module is Monel alloy, the mass transfer coefficient of the reactor is20 Ka, and the heat exchange capacity is 2000Kw/m2·K。
Example 1
The toluene solution of vinyl ethyl ether as a reaction raw material and trifluoroacetyl chloride as a raw material enter a reaction module of a microchannel reactor, the temperature of a heat exchanger is set to be 0 ℃, namely the reaction temperature is 0 ℃, and the reaction pressure is set to be 0 MPa. The feeding speed of the toluene solution of vinyl ethyl ether is 2g/min, the mass concentration of the vinyl ethyl ether is 30%, the feeding speed of trifluoroacetyl chloride is 1.10g/min, and the molar ratio of the vinyl ethyl ether to the trifluoroacetyl chloride is 1:1. Respectively collecting liquid and gas obtained at the outlet of the microchannel reaction module, heating the liquid (crude product) to 60 ℃ to remove HCl to obtain the product 4-ethoxy-1, 1, 1-trifluoro-butene-2-ketone, wherein the content after rectification is 99.1 percent, and the yield is 95.1 percent.
Example 2
The dichloromethane solution of the reaction raw material 3-dimethylamino ethyl acrylate and the raw material trifluoroacetyl chloride enter a reaction module of the microchannel reactor, the temperature of a heat exchanger is set to be 10 ℃, namely the reaction temperature is 10 ℃, and the reaction pressure is set to be 0.01 MPa. The feeding speed of the dichloromethane solution of the 3-dimethylamino ethyl acrylate is 4g/min, the mass concentration of the 3-dimethylamino ethyl acrylate is 20%, the feeding speed of the trifluoroacetyl chloride is 0.82g/min, and the molar ratio of the 3-dimethylamino ethyl acrylate to the trifluoroacetyl chloride is 1: 1.1. Respectively collecting liquid and gas obtained at the outlet of the microchannel reaction module, heating the liquid (crude product) to 80 ℃ to remove HCl to obtain a product 2-dimethylamino methylene-4, 4, 4-trifluoro-3-oxo-butyric acid ethyl ester, wherein the content of the product is 99.0 percent after the product is crystallized by using cyclohexane, and the yield is 93.1 percent.
Example 3
The acetonitrile solution of propenyl ether as a reaction raw material and trifluoroacetyl chloride as a raw material enter a reaction module of a microchannel reactor, the temperature of a heat exchanger is set to be-10 ℃, namely the reaction temperature is-10 ℃, and the reaction pressure is set to be 0 MPa. The feeding speed of the acetonitrile solution of propenyl diethyl ether is 3g/min, the mass concentration of the propenyl diethyl ether is 20%, the feeding speed of trifluoroacetyl chloride is 1.11g/min, and the molar ratio of propenyl diethyl ether to trifluoroacetyl chloride is 1: 1.2. Respectively collecting liquid and gas obtained at the outlet of the microchannel reaction module, heating the liquid (crude product) to 80 ℃ to remove HCl to obtain the product 4-ethoxy-3-methyl-1, 1, 1-trifluoro-butene-2-ketone, wherein the content of the rectified product is 99.30 percent, and the yield is 96.1 percent.
Example 4
The dichloroethane solution of the reaction raw material 4-bromo-3-ethoxy-2-ethyl crotonate and the raw material trifluoroacetyl chloride enter a reaction module of the microchannel reactor, the temperature of the heat exchanger is set to be 10 ℃, namely the reaction temperature is 10 ℃, and the reaction pressure is set to be 0 MPa. The feed rate of the dichloroethane solution of the 4-bromo-3-ethoxy-2-ethyl crotonate is 5g/min, the mass concentration of the 4-bromo-3-ethoxy-2-ethyl crotonate is 20%, the feed rate of trifluoroacetyl chloride is 0.56g/min, and the molar ratio of the 4-bromo-3-ethoxy-2-ethyl crotonate to the trifluoroacetyl chloride is 1: 1.1. Respectively collecting liquid and gas obtained at an outlet of the microchannel reaction module, heating the liquid (crude product) to 100 ℃ to remove HCl to obtain a product of 4-bromo-3-ethoxy-2-trifluoroacetyl-2-ethyl crotonate, and crystallizing by using n-hexane to obtain the product with the content of 99.01 percent and the yield of 95.2 percent.
Example 5
The toluene solution of the reaction raw material 1- (trimethylsiloxy) cyclopentene and the raw material trifluoroacetyl chloride enter a reaction module of a microchannel reactor, the temperature of a heat exchanger is set to be 0 ℃, namely the reaction temperature is 0 ℃, and the reaction pressure is set to be 0 MPa. The feeding speed of the toluene solution of the 1- (trimethylsiloxy) cyclopentene was 4g/min, the mass concentration of the 1- (trimethylsiloxy) cyclopentene was 25%, the feeding speed of trifluoroacetyl chloride was 0.85g/min, and the molar ratio of the 1- (trimethylsiloxy) cyclopentene to the trifluoroacetyl chloride was 1:1. Respectively collecting liquid and gas obtained at the outlet of the microchannel reaction module, heating the liquid (crude product) to 90 ℃ to remove HCl to obtain the product 1- (trimethylsiloxy) -2-trifluoroacetyl cyclopentene, wherein the content of the rectified product is 99.1 percent, and the yield is 92.2 percent.
Example 6
The toluene solution of the reaction raw material 1, 1-bis (trimethylsilyl oxide) -3-methyl-1-butene and the raw material trifluoroacetyl chloride enter a reaction module of a microchannel reactor, the temperature of a heat exchanger is set to be 5 ℃, namely the reaction temperature is set to be 5 ℃, and the reaction pressure is set to be 0 MPa. The feeding speed of the toluene solution of the 1, 1-bis (trimethylsilyloxy) -3-methyl-1-butene is 4g/min, the mass concentration of the 1, 1-bis (trimethylsilyloxy) -3-methyl-1-butene is 30%, the feeding speed of trifluoroacetyl chloride is 0.71g/min, and the molar ratio of the 1, 1-bis (trimethylsilyloxy) -3-methyl-1-butene to the trifluoroacetyl chloride is 1: 1.1. Respectively collecting liquid and gas obtained at the outlet of the microchannel reaction module, heating the liquid (crude product) to 90 ℃ to remove HCl to obtain the product 1, 1-bis (trimethylsilyl oxide) -3-methyl-2-trifluoroacetyl-1-butene, and crystallizing by using acetonitrile to obtain the product with the content of 99.01 percent and the yield of 90.2 percent.
Comparative example 1
30g of vinyl ethyl ether and 70g of toluene solvent are added into a reaction kettle, the reaction temperature is controlled to be 0 ℃, and the reaction pressure is 0 MPa. Trifluoroacetyl chloride is fed into the reactor at a feeding speed of 1.1g/min, 55.2g of trifluoroacetyl chloride is continuously fed into the reactor, after the reaction is finished, the obtained liquid crude product is heated to 60 ℃ to remove HCl, the conversion rate of vinyl ethyl ether is monitored by GC to be 40%, and the product 4-ethoxy-1, 1, 1-trifluoro-butene-2-ketone is obtained through rectification, wherein the content is 99.0%, and the yield is 25.1%.
Comparative example 2
30g of 3-dimethylamino ethyl acrylate and 70g of dichloromethane solvent are added into a reaction kettle, the reaction temperature is controlled to be 0 ℃, and the reaction pressure is kept to be 0 MPa. Trifluoroacetyl chloride is fed into the reactor at a feeding speed of 1.1g/min, 27.8g of trifluoroacetyl chloride is continuously fed into the reactor, after the reaction is finished, the obtained liquid crude product is heated to 60 ℃ to remove HCl, the conversion rate of 3-dimethylamino ethyl acrylate is monitored to be 20% by GC, and cyclohexane is used to obtain a product of 2-dimethylamino methylidyne-4, 4, 4-trifluoro-3-oxoethyl butyrate, wherein the content is 97.0%, and the yield is 15.1%.
Comparative example 3
30g of propenyl ether and 70g of acetonitrile solvent are added into a reaction kettle, the reaction temperature is controlled to be 0 ℃, and the reaction pressure is kept to be 0 MPa. And (3) introducing trifluoroacetyl chloride into the reaction kettle at the feeding speed of 1.1g/min, continuously introducing 46.22g of trifluoroacetyl chloride, after the reaction is finished, heating the obtained liquid crude product to 60 ℃ to remove HCl, and monitoring the conversion rate of propenyl diethyl ether to be 0% by GC (gas chromatography), wherein no product is generated.
Claims (10)
1. A continuous preparation method of trifluoromethyl butenone derivatives is characterized in that: reacting a raw material 1 shown in a structure (I) in the following reaction formula with trifluoroacetyl halide serving as a raw material 2 in a microchannel reactor to prepare the trifluoromethyl butenone derivative shown in a structure (II):
wherein R is an electron donating group and can be conjugated with an olefin double bond; r1、R2Independently selected from hydrogen, C1-C20 alkyl, aryl or substituted aryl or silyl; x is halogen selected from fluorine, chlorine, bromine or iodine.
2. The continuous preparation method of trifluoromethyl butenone derivative according to claim 1, characterized in that: the R is selected from any one of the following structures:
wherein Q1, Q2, Q3 and Q4 are independently selected from-CnH2n+2，-CnH2n，-CnH2n-2-Ar, -COR ', -COOR ', wherein n is greater than or equal to 12 and is greater than or equal to 2, and R ' is alkyl with the carbon number less than 12.
3. The continuous preparation method of trifluoromethylbutenone derivatives according to claim 1 or 2, characterized in that: the continuous preparation method comprises the following steps:
A1. the raw material 1 and the raw material 2 enter a reaction module of a microchannel reactor, the reaction temperature is-20-30 ℃, the reaction pressure is 0-1.0 Mpa, the molar ratio of the raw material 1 to the raw material 2 is 1: 1-1.5, and the flow rate of the raw material 1 is 1-50 g/min;
A2. and collecting the reaction liquid at the outlet of the reaction module to obtain a liquid part and a gas part, and heating the liquid part to remove the hydrogen halide therein to obtain the trifluoromethyl butenone derivative.
4. The continuous production method of trifluoromethylbutenone derivatives according to claim 3, wherein: the raw material 1 is selected from ethoxy vinyl ether, 1-methoxy propylene ether, 2-methoxy propylene ether or 3- (dimethylamino) ethyl acrylate; the trifluoroacetyl halide is selected from trifluoroacetyl chloride or trifluoroacetyl fluoride.
5. The continuous production method of trifluoromethylbutenone derivatives according to claim 3, wherein: and the heating temperature of the liquid part in the step A2 is 20-100 ℃, and the trifluoromethyl butenone derivative with the purity of more than 99 percent is obtained.
6. The continuous production method of trifluoromethylbutenone derivatives according to claim 3, wherein: the molar ratio of the raw material 1 to the raw material 2 is 1: 1-1.2, the flow rate of the raw material 1 is 20-40 g/min, the reaction pressure is 0-0.5 MPa, and the reaction temperature is-10-20 ℃.
7. The continuous production method of trifluoromethylbutenone derivatives according to claim 3, wherein: the raw material 1 is dissolved in a solvent and then enters a reaction module, and the solvent is selected from at least one of toluene, dichloromethane, acetonitrile and dichloroethane.
8. The continuous production method of trifluoromethylbutenone derivatives according to claim 3, wherein: the mass transfer coefficient of the microchannel reactor is 1-30 Ka, and the heat exchange is carried outCapacity of 1700Kw/m2K or more.
9. The continuous preparation method of trifluoromethylbutenone derivatives as claimed in claim 8, wherein: the material of the reaction module is selected from silicon carbide, Hash alloy or Monel alloy.
10. The continuous process for the preparation of trifluoromethylbutenone derivatives according to any of the claims 1 to 9, wherein: the micro-channel structure in the reaction module comprises a straight-flow channel structure and an enhanced mixed type channel structure, the straight-flow channel structure is a tubular structure, the enhanced mixed type channel structure is a T-shaped structure, a spherical structure, a water-drop-shaped structure or a heart-shaped structure, and the equivalent diameter of the enhanced mixed type channel is 0.5-10 mm.
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| CN1832911A (en) * | 2003-06-06 | 2006-09-13 | 苏威氟有限公司 | Method for producing alkenone ethers |
| CN102112428A (en) * | 2008-07-04 | 2011-06-29 | 索尔维公司 | Process for the manufacture of alkenones |
| EP2360136A1 (en) * | 2002-02-08 | 2011-08-24 | Solvay Fluor GmbH | Production of alkenones |
| CN102341361A (en) * | 2009-03-04 | 2012-02-01 | 先正达参股股份有限公司 | Chemical process for the production of haloalkenone ethers |
| WO2012025548A1 (en) * | 2010-08-27 | 2012-03-01 | Solvay Sa | Process for the preparation of alkenones |
| CN104583167A (en) * | 2012-08-22 | 2015-04-29 | 索尔维公司 | Process for the manufacture of alkenones |
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| EP2360136A1 (en) * | 2002-02-08 | 2011-08-24 | Solvay Fluor GmbH | Production of alkenones |
| CN1832911A (en) * | 2003-06-06 | 2006-09-13 | 苏威氟有限公司 | Method for producing alkenone ethers |
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| CN102341361A (en) * | 2009-03-04 | 2012-02-01 | 先正达参股股份有限公司 | Chemical process for the production of haloalkenone ethers |
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