CN106045836A - Method for synthesizing aromatic hydrocarbon or heterocyclic trifluoromethylketone under catalytic action of copper - Google Patents
Method for synthesizing aromatic hydrocarbon or heterocyclic trifluoromethylketone under catalytic action of copper Download PDFInfo
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- CN106045836A CN106045836A CN201610493675.3A CN201610493675A CN106045836A CN 106045836 A CN106045836 A CN 106045836A CN 201610493675 A CN201610493675 A CN 201610493675A CN 106045836 A CN106045836 A CN 106045836A
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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
- C07C45/61—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
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- C07—ORGANIC CHEMISTRY
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses a method for synthesizing aromatic hydrocarbon or heterocyclic trifluoromethylketone under the catalytic action of copper. The method comprises the following steps: by using cuprous oxide or cuprous sulfide as a catalyst, stirring aromatic hydrocarbon or heterocyclic diazonium salt and alkyl trifluoroacetonate in a dimethyl sulfoxide-dichloromethane mixed solvent at room temperature for 1-16 hours; and after the reaction finishes, carrying out after-treatment on the reaction solution to obtain the aromatic hydrocarbon or heterocyclic trifluoromethylketone compound. The synthesis method has the advantages of cheap and accessible catalyst, low catalyst toxicity, mild reaction conditions, accessible raw materials, favorable functional group universality and the like, and is simple to operate.
Description
Technical field
The invention belongs to organic fluorine chemistry synthesis field, be specifically related to a kind of copper and catalyze and synthesize aromatic hydrocarbons or heterocycle trifluoromethyl
The method of ketone.
Background technology
Trifluoromethyl, owing to having the most electron-withdrawing and high lipophilic, therefore shows many non-containing trifluoromethyl compound
The physical property of Chang Dute and chemical property.After introducing trifluoromethyl in molecule, can significantly change the polarity of molecule, reduction
PKa value and raising membrane permeability, also have impact on metabolic pathway and the Pharmacokinetic Characteristics of molecule simultaneously.Containing trifluoromethyl chemical combination
Thing is widely used in medicine, pesticide and Material Field.Wherein trifluoromethyl ketonic compound shows significantly
Suppress the activity of various esterase and protease, be also the important medicine intermediate of a class.Build and have containing trifluoromethyl ketonic compound
There is important theoretical significance, it may have economic worth.But, existing synthetic method, there is severe reaction conditions, step
The most loaded down with trivial details, expensive reagents, the shortcomings such as substrate spectrum is narrow.Therefore invent and a kind of utilize Material synthesis simple and easy to get, cheap virtue
Hydrocarbon or the method for heterocycle trifluoromethyl ketonic compound, be one of the study hotspot of organic fluorine chemistry.
Summary of the invention
It is an object of the invention to provide a kind of method that copper catalyzes and synthesizes aromatic hydrocarbons (heterocycle) trifluoromethyl ketone, this method raw material
Cheap and easy to get, productivity is the highest, and the adaptability of functional group is fine, and its operation is easy, has good commercial Application
Prospect.
For achieving the above object, the present invention adopts the following technical scheme that
。
A kind of copper catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, with Red copper oxide or cuprous sulfide for catalysis
Agent, with trifluoroacetone acid alkyl ester and aromatic diazonium salt or heterocycle diazol as raw material, at dimethyl sulfoxide and dichloromethane
In mixed solvent, reaction prepares aromatic hydrocarbons or heterocycle trifluoromethyl ketone；The structural formula of described aromatic diazonium salt is:；The structural formula of described heterocycle diazol is:。
The described aromatic moieties in aromatic diazonium salt structural formula is any one in following formula 1-formula 25:
；
The described heterocyclic moiety in heterocycle diazol structural formula is any one in following formula 26-formula 30:
。
Described trifluoroacetone acid alkyl ester is trifluoropropyl keto acid methyl ester or trifluoroacetone acetoacetic ester.
The mol ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1-1:
0.4-4:0.8-8:1.2-12。
Preferably, the mol ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is
0.1:0.4:0.8:1.2。
In described dimethyl sulfoxide and the mixed solvent of dichloromethane, dimethyl sulfoxide and the volume ratio of dichloromethane
For: 1-3:1-50.
Specifically comprise the following steps that in nitrogen atmosphere, in the container with magnetic stirring apparatus add catalyst, aromatic hydrocarbons or
Heterocycle diazol, trifluoroacetone acid alkyl ester and mixed solvent, shut stopper after mix homogeneously, put it into and continue to stir under room temperature
Mixing 1-16 hour, extract with ether, merge organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters,
Then rotation is evaporated off organic solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains
Aromatic hydrocarbons or heterocycle trifluoromethyl ketone product.
The beneficial effects of the present invention is:
The present invention is with aromatic hydrocarbons (heterocycle) diazol cheap and easy to get, trifluoropropyl keto acid methyl ester or trifluoroacetone acetoacetic ester etc. for former
Material, synthesizes aromatic hydrocarbons (heterocycle) trifluoromethyl ketone with Red copper oxide or cuprous sulfide for catalyst, obtains the highest productivity, official
The adaptability that can roll into a ball is fine, and its operation is easy, has good prospects for commercial application.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention to technology of the present invention
Scheme is described further, but the present invention is not limited only to this.
Embodiment 1
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol benzene diazonium tetrafluoro
Borate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2 mmol tri-
Fluoropyruvate ethyl ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL, merges organic
Phase, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；Obtain is thick
Product passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains α, and α, α-trifluoroacetophenone (separates productivity
86%).1H NMR (400 MHz, CDCl3) δ 8.10 (dd, J = 7.5, 1.1 Hz, 2H), 7.77 – 7.71 (m,
1H), 7.61 – 7.54 (m, 2H)；19F NMR (376 MHz, CDCl3) δ -71.46 (s)；GC-MS m/z 174
(M+)。
Embodiment 2
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol to methylbenzene weight
Nitrogen tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2
Mmol trifluoroacetone acetoacetic ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL,
Merging organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；
The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 4-(trifluoroacetyl group) toluene and (divides
From productivity 86%).1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 7.8 Hz, 2H), 7.36 (d, J =
8.1 Hz, 2H), 2.48 (s, 3H)；19F NMR (376 MHz, CDCl3) δ -71.37 (s)；GC-MS m/z 188
(M+)。
Embodiment 3
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 3,4-dimethoxy
Base benzene diazonium tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, finally add
Enter 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, extract 3 times with ether, every time
10 mL, merge organic facies, and with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filter, and then rotation is evaporated off organic
Solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 1-(3,4-dimethoxy-benzenes
Base)-2,2,2-trifluoroethanone (separating productivity 85%).1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.6 Hz,
1H), 7.57 (d, J = 1.7 Hz, 1H), 6.96 (d, J = 8.6 Hz, 1H), 3.99 (s, 3H), 3.95
(s, 3H)；19F NMR (376 MHz, CDCl3) δ -70.48 (s)；GC-MS m/z 234 (M+)。
Embodiment 4
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 3,5-dimethyl
Benzene diazonium tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding
1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, extract 3 times with ether, and each 10
ML, merges organic facies, and with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic molten
Agent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 3', 5'-dimethyl-2, and 2,
2-trifluoroacetophenone (separates productivity 82%).1H NMR (400 MHz, CDCl3) δ 7.70 (s, 2H), 7.36 (s,
1H), 2.43 (d, J= 0.6 Hz, 6H)；19F NMR (376 MHz, CDCl3) δ -71.23 (s)；GC-MS m/z
202 (M+)。
Embodiment 5
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 4-phenyl benzene weight
Nitrogen tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2
Mmol trifluoroacetone acetoacetic ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL,
Merging organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；
The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 4'-phenyl-2,2,2-trifluoro-benzenes
Ethyl ketone (separates productivity 88%).1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.0 Hz, 2H), 7.80
(dd, J = 8.4, 1.4 Hz, 2H), 7.68 (dd, J = 6.7, 1.4 Hz, 2H), 7.54 (dd, J =
10.7, 3.8 Hz, 2H), 7.48 (dd, J= 9.6, 4.0 Hz, 1H)；19F NMR (376 MHz, CDCl3) δ -
71.32 (s)；GC-MS m/z 250 (M+)。
Embodiment 6
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 3,4,5-front three
Epoxide benzene diazonium tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, finally
Add 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, extract 3 times with ether, often
Secondary 10 mL, merge organic facies, and with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filter, and then rotation has been evaporated off
Machine solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 3'4'5'-trimethoxy
Base-2,2,2-trifluoroacetophenone (separates productivity 78%).1H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 0.8
Hz, 2H), 3.99 (s, 3H), 3.94 (s, 6H)；19F NMR (376 MHz, CDCl3) δ -70.52 (s)；GC-
MS m/z 264 (M+)。
Embodiment 7
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 4-methoxybenzene
Diazonium tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2
Mmol trifluoroacetone acetoacetic ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL,
Merging organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；
The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 4'-methoxyl group-2,2,2-trifluoros
1-Phenylethanone. (separates productivity 88%).1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.3 Hz, 2H), 7.03
(d, J= 9.0 Hz, 2H), 3.94 (s, 3H)；19F NMR (376 MHz, CDCl3) δ -71.01 (s)；GC-MS
m/z 204 (M+)。
Embodiment 8
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 2-naphthalene diazonium four
Borofluoride, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2 mmol
Trifluoroacetone acetoacetic ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL, is associated with
Machine phase, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；Obtain
Crude product passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 1-(2-naphthyl)-2,2,2-trifluoroethanone
(separating productivity 75%).1H NMR (400 MHz, CDCl3) δ 8.62 (s, 1H), 8.07 (dd, J = 8.7, 1.1
Hz, 1H), 8.01 (dd, J = 8.2, 0.6 Hz, 1H), 7.95 (d, J = 8.8 Hz, 1H), 7.90 (dd,J = 8.2, 0.4 Hz, 1H), 7.69 (ddd, J = 8.2, 6.9, 1.3 Hz, 1H), 7.61 (ddd, J =
8.1, 6.9, 1.3 Hz, 1H)；19F NMR (376 MHz, CDCl3) δ -70.74 (s)；GC-MS m/z 224 (M+)。
Embodiment 9
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 4-iodobenzene diazonium
Tetrafluoroborate, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, it is eventually adding 1.2
Mmol trifluoroacetone acetoacetic ester, in enclosed system after 25 ° of C stirring reaction 16 h, extracts 3 times with ether, each 10 mL,
Merging organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, and then rotation is evaporated off organic solvent；
The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains iodo-2,2, the 2-trifluoro-benzene second of 4'-
Ketone (separates productivity 66%).1H NMR (400 MHz, CDCl3) δ 7.99 – 7.93 (m, 2H), 7.79 (d, J =
7.9 Hz, 2H)；19F NMR (376 MHz, CDCl3) δ -71.56 (s)；GC-MS m/z 300 (M+)。
Embodiment 10
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 2-methoxyl group-
5-Tetrafluoroboric acid diazonium pyridine, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, finally add
Enter 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, extract 3 times with ether, every time
10 mL, merge organic facies, and with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filter, and then rotation is evaporated off organic
Solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 2,2,2-tri-fluoro-1-[3-
(6-methoxyl group) pyridine radicals] ethyl ketone (separating productivity 54%).1H NMR (400 MHz, CDCl3) δ 8.94 (s, 1H),
8.23 (d, J = 8.9 Hz, 1H), 6.89 (d, J= 8.9 Hz, 1H), 4.08 (s, 3H)；19F NMR (376
MHz, CDCl3) δ -71.85 (s)；GC-MS m/z 205 (M+)。
Embodiment 11
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 2-chloro-3-first
Base-5-Tetrafluoroboric acid diazonium pyridine, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide, finally
Add 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, extract 3 times with ether, often
Secondary 10 mL, merge organic facies, and with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filter, and then rotation has been evaporated off
Machine solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 1-(6'-chloro-5'-first
Base-3'-pyridine radicals)-2,2,2-trifluoroethanone (separating productivity 30%).1H NMR (400 MHz, CDCl3) δ 8.90 (s,
1H), 8.20 (s, 1H), 2.52 (s, 3H)。19F NMR (376 MHz, CDCl3) δ -72.39 (s)。GC-MS m/
z 223 (M+)。
Embodiment 12
In nitrogen atmosphere, a reactor is put into politef Magnetitum one, add 0.4 mmol 2-(2'-benzo
Thiophene)-3-methyl-5-Tetrafluoroboric acid diazonium pyridine, 0.1 mmol Red copper oxide, 1 mL dichloromethane, 0.8 mmol diformazan
Base sulfoxide, is eventually adding 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 ° of C stirring reaction 16 h, uses ether
Extracting 3 times, each 10 mL, merge organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, then
Rotation is evaporated off organic solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains 1-
(6'-(2''-benzothiophene)-5'-methyl-3'-pyridine radicals)-2,2,2-trifluoroethanone (separates productivity 50%).1H NMR (400
MHz, CDCl3) δ 9.17 (s, 1H), 8.22 (d, J = 0.6 Hz, 1H), 7.95 (s, 1H), 7.94 –
7.86 (m, 2H), 7.52 – 7.34 (m, 2H), 2.82 (s, 3H)。19F NMR (376 MHz, CDCl3) δ -
72.07 (s)。GC-MS m/z 321 (M+)。
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (7)
1. a copper catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that: with Red copper oxide or sulfuration Asia
Copper is catalyst, with trifluoroacetone acid alkyl ester and aromatic diazonium salt or heterocycle diazol as raw material, at dimethyl sulfoxide and two
In the mixed solvent of chloromethanes, reaction prepares aromatic hydrocarbons or heterocycle trifluoromethyl ketone；The structural formula of described aromatic diazonium salt is:；The structural formula of described heterocycle diazol is:。
A kind of copper the most according to claim 1 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
The described aromatic moieties in aromatic diazonium salt structural formula is any one in following formula 1-formula 25:
；
The described heterocyclic moiety in heterocycle diazol structural formula is any one in following formula 26-formula 30:
。
A kind of copper the most according to claim 1 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
Described trifluoroacetone acid alkyl ester is trifluoropropyl keto acid methyl ester or trifluoroacetone acetoacetic ester.
A kind of copper the most according to claim 1 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
The mol ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1-1:0.4-4:
0.8-8:1.2-12。
A kind of copper the most according to claim 4 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
The mol ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1:0.4:0.8:
1.2。
A kind of copper the most according to claim 1 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
In described dimethyl sulfoxide and the mixed solvent of dichloromethane, the volume ratio of dimethyl sulfoxide and dichloromethane is: 1-3:1-
50。
A kind of copper the most according to claim 1 catalyzes and synthesizes aromatic hydrocarbons or the method for heterocycle trifluoromethyl ketone, it is characterised in that:
Specifically comprise the following steps that in nitrogen atmosphere, in the container with magnetic stirring apparatus, add catalyst, aromatic hydrocarbons or heterocycle diazonium
Salt, trifluoroacetone acid alkyl ester and mixed solvent, shut stopper after mix homogeneously, puts it into continuation stirring 1-16 under room temperature little
Time, extract with ether, merge organic facies, with distilled water wash 3 times, organic facies anhydrous magnesium sulfate is dried, and filters, then revolves steaming
Remove organic solvent；The crude product obtained passes through silica gel column chromatography, carries out eluting with pentane for eluant, obtains aromatic hydrocarbons or miscellaneous
Ring trifluoromethyl ketone product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946758A (en) * | 2017-03-07 | 2017-07-14 | 丽水学院 | A kind of synthetic method of 3 (trifluoroacetyl) indole derivativeses |
| CN111116368A (en) * | 2020-01-15 | 2020-05-08 | 河南师范大学 | Green preparation method of aryl α -keto acid ester compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147256A (en) * | 1994-05-05 | 1997-04-09 | 默里尔药物公司 | Process for preparation of 1-(3-trialkyl-silylphenyl)-2,2,2-trifluoromethylethanone derivs |
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Patent Citations (1)
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| CN1147256A (en) * | 1994-05-05 | 1997-04-09 | 默里尔药物公司 | Process for preparation of 1-(3-trialkyl-silylphenyl)-2,2,2-trifluoromethylethanone derivs |
Non-Patent Citations (3)
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| GREGORY DANOUN ET AL.: "Sandmeyer Trifluoromethylation of Arenediazonium Tetrafluoroborates", 《ANGEW. CHEM. INT. ED.》 * |
| WEI WU ET AL.: "Copper-Mediated Trifluoroacetylation of Arenediazonium Salts with Ethyl Trifluoropyruvate", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| ZHIQIANG WENG ET AL.: "An Air-Stable Copper Reagent for Nucleophilic Trifluoromethylthiolation of Aryl Halides", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946758A (en) * | 2017-03-07 | 2017-07-14 | 丽水学院 | A kind of synthetic method of 3 (trifluoroacetyl) indole derivativeses |
| CN106946758B (en) * | 2017-03-07 | 2019-11-19 | 丽水学院 | A kind of synthetic method of 3- (trifluoroacetyl) indole derivatives |
| CN111116368A (en) * | 2020-01-15 | 2020-05-08 | 河南师范大学 | Green preparation method of aryl α -keto acid ester compound |
| CN111116368B (en) * | 2020-01-15 | 2022-07-22 | 河南师范大学 | Green preparation method of aryl alpha-keto acid ester compound |
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| CN106045836B (en) | 2018-04-13 |
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