CN106045836B - A kind of method of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone - Google Patents

A kind of method of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone Download PDF

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CN106045836B
CN106045836B CN201610493675.3A CN201610493675A CN106045836B CN 106045836 B CN106045836 B CN 106045836B CN 201610493675 A CN201610493675 A CN 201610493675A CN 106045836 B CN106045836 B CN 106045836B
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heterocycle
aromatic hydrocarbons
trifluoromethyl ketone
diazol
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CN106045836A (en
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翁志强
吴伟
张云霄
田沁丽
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Fuzhou University
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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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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 the method for a kind of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone：Using cuprous oxide or cuprous sulfide as catalyst, using aromatic hydrocarbons or heterocycle diazol and trifluoroacetone acid alkyl ester as raw material, in the in the mixed solvent of dimethyl sulfoxide (DMSO) and dichloromethane, when stirring 1 ~ 16 is small at room temperature, reaction solution is post-processed after reaction and obtains aromatic hydrocarbons or heterocycle trifluoromethyl ketone compound.The advantages that synthetic method of the present invention has catalyst cheap and easy to get and small toxicity, and reaction condition is gentle, raw material is easy to get, easy to operate, and functional group's universality is good.

Description

A kind of method of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone
Technical field
The invention belongs to organic fluorine chemistry to synthesize field, and in particular to a kind of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl The method of ketone.
Background technology
Trifluoromethyl containing trifluoromethyl compound due to strong electron-withdrawing and high lipophilic, showing many non- The physical property and chemical property of Chang Dute.After introducing trifluoromethyl into molecule, it can significantly change the polarity of molecule, reduce PKa values and raising membrane permeability, while also have impact on the metabolic pathway and Pharmacokinetic Characteristics of molecule.Chemical combination containing trifluoromethyl Thing is widely used in medicine, pesticide and Material Field.Wherein trifluoromethyl ketone compound is shown significantly Suppress the activity of various esterases and protease, and a kind of important medicine intermediate.Build the tool of ketone compound containing trifluoromethyl There is important theoretical significance, it may have economic value.However, existing synthetic method, there is severe reaction conditions, step It is rapid cumbersome, the shortcomings of expensive reagents, substrate spectrum is narrow.Simple and easy to get, cheap Material synthesis virtue is utilized because the invention is a kind of The method of hydrocarbon or heterocycle trifluoromethyl ketone compound, is one of research hotspot of organic fluorine chemistry.
The content of the invention
It is an object of the invention to provide a kind of method of copper catalysis synthesis aromatic hydrocarbons (heterocycle) trifluoromethyl ketone, the method raw material Cheap and easy to get, yield is generally higher, and the adaptability of functional group is fine, and its operation is easy, has good commercial Application Prospect.
To achieve the above object, the present invention adopts the following technical scheme that：
。
A kind of method of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone, using cuprous oxide or cuprous sulfide as catalysis Agent, using trifluoroacetone acid alkyl ester and aromatic diazonium salt or heterocycle diazol as raw material, in dimethyl sulfoxide (DMSO) and dichloromethane In the mixed solvent, reacts and aromatic hydrocarbons or heterocycle trifluoromethyl ketone is made；The structural formula of the aromatic diazonium salt is：；The structural formula of the heterocycle diazol is：。
Aromatic moieties in the aromatic diazonium salt structural formula are any one in following formula 1- formulas 25：
；
Heterocyclic moiety in the heterocycle diazol structural formula is any one in following formula 26- formulas 30：
。
The trifluoroacetone acid alkyl ester is trifluoropropyl ketone acid methyl esters or trifluoroacetone acetoacetic ester.
The molar 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 molar ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1:0.4:0.8:1.2。
The volume ratio of the dimethyl sulfoxide (DMSO) and the in the mixed solvent of dichloromethane, dimethyl sulfoxide (DMSO) and dichloromethane For：1-3:1-50.
Comprise the following steps that：In nitrogen atmosphere, into the container with magnetic stirring apparatus add catalyst, aromatic hydrocarbons or Heterocycle diazol, trifluoroacetone acid alkyl ester and mixed solvent, shut plug after mixing, put it into and continue to stir at room temperature Mix 1-16 it is small when, extracted with ether, merge organic phase, be washed with distilled water 3 times, organic phase is dried with anhydrous magnesium sulfate, filtering, Then revolving removes organic solvent；Obtained crude product is eluted by eluant, eluent of pentane, obtained by silica gel column chromatography Aromatic hydrocarbons or heterocycle trifluoromethyl ketone product.
The beneficial effects of the present invention are：
It is of the invention to be with aromatic hydrocarbons (heterocycle) diazol, trifluoropropyl ketone acid methyl esters or trifluoroacetone acetoacetic ester cheap and easy to get etc. Raw material, aromatic hydrocarbons (heterocycle) trifluoromethyl ketone is synthesized using cuprous oxide or cuprous sulfide as catalyst, obtains universal higher yield, The adaptability of functional group is fine, and its operation is easy, has good prospects for commercial application.
Embodiment
In order to make content of the present invention easily facilitate understanding, with reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
In nitrogen atmosphere, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol benzene diazonium Tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, are eventually adding 1.2 Mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, are extracted 3 times, every time 10 mL with ether, Merge organic phase, be washed with distilled water 3 times, organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic solvent； Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains α, α, α-trifluoroacetophenone（Separation Yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol to methyl Benzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, are eventually adding 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, 3 times are extracted with ether, and every time 10 ML, merges organic phase, is washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic molten Agent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 4- (trifluoroacetyl group) toluene （Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 3,4- bis- Methoxybenzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, most After add 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system 25 °C stirring reaction 16 h after, with ether extract 3 times, 10 mL every time, merges organic phase, is washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes Organic solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 1- (3,4- diformazans Oxygen phenyl) -2,2,2- trifluoroethanones（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 3,5- bis- Methylbenzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, finally Add 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system 25 °C stirring reaction 16 h after, with ether extract 3 times, often Secondary 10 mL, merges organic phase, is washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then rotating removing has Solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 3', and 5'- dimethyl- 2,2,2- trifluoroacetophenones（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 4- phenyl Benzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, are eventually adding 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, 3 times are extracted with ether, and every time 10 ML, merges organic phase, is washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic molten Agent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 4'- phenyl -2,2,2- trifluoros Acetophenone（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 3,4,5- Trimethoxy-benzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, 1.2 mmol trifluoroacetone acetoacetic esters are eventually adding, in enclosed system after 25 °C of 16 h of stirring reaction, 3 are extracted with ether Secondary, 10 mL, merges organic phase, is washed with distilled water 3 times every time, and organic phase is dried with anhydrous magnesium sulfate, and filtering, then rotates Remove organic solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 3'4'5'- Trimethoxy -2,2,2- trifluoroacetophenones（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 4- methoxies Base benzene diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, finally add Enter 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system 25 °C stirring reaction 16 h after, with ether extract 3 times, every time 10 mL, merge organic phase, are washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic Solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 4'- methoxyl groups -2,2,2- Trifluoroacetophenone（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 2- naphthalene weights Nitrogen tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, are eventually adding 1.2 Mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, are extracted 3 times, every time 10 mL with ether, Merge organic phase, be washed with distilled water 3 times, organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic solvent； Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 1- (2- naphthyls) -2,2,2- trifluoros Ethyl ketone（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 4- iodobenzenes Diazonium tetrafluoroborate, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, are eventually adding 1.2 Mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, are extracted 3 times, every time 10 mL with ether, Merge organic phase, be washed with distilled water 3 times, organic phase is dried with anhydrous magnesium sulfate, filtering, and then revolving removes organic solvent； Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains iodo- 2,2,2- trifluoro-benzene second of 4'- Ketone（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 2- methoxies Base -5- tetrafluoro boric acid diazonium pyridines, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, finally Add 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system 25 °C stirring reaction 16 h after, with ether extract 3 times, often Secondary 10 mL, merges organic phase, is washed with distilled water 3 times, and organic phase is dried with anhydrous magnesium sulfate, filtering, and then rotating removing has Solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 2,2,2- tri- fluoro- 1- [3- (6- methoxyl groups) pyridine radicals] ethyl ketone（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, it is chloro- to add 0.4 mmol 2- 3- methyl -5- tetrafluoro boric acid diazonium pyridines, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol dimethyl sulfoxide (DMSO)s, 1.2 mmol trifluoroacetone acetoacetic esters are eventually adding, in enclosed system after 25 °C of 16 h of stirring reaction, 3 are extracted with ether Secondary, 10 mL, merges organic phase, is washed with distilled water 3 times every time, and organic phase is dried with anhydrous magnesium sulfate, and filtering, then rotates Remove organic solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains 1- (6'- Chloro- 5'- methyl -3'- pyridine radicals) -2,2,2- trifluoroethanones（Separate yield 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, polytetrafluoroethylene (PTFE) magnetite one is put into a reactor, adds 0.4 mmol 2- (2'- Benzothiophene) -3- methyl -5- tetrafluoro boric acid diazonium pyridines, 0.1 mmol cuprous oxide, 1 mL dichloromethane, 0.8 mmol Dimethyl sulfoxide (DMSO), is eventually adding 1.2 mmol trifluoroacetone acetoacetic esters, in enclosed system after 25 °C of 16 h of stirring reaction, uses Ether extracts 3 times, and 10 mL, merges organic phase, be washed with distilled water 3 times every time, and organic phase is dried with anhydrous magnesium sulfate, filtering, Then revolving removes organic solvent；Obtained crude product is eluted by eluant, eluent of pentane, obtained by silica gel column chromatography 1- (6'- (2''- benzothiophenes) -5'- methyl -3'- pyridine radicals) -2,2,2- trifluoroethanones（Separate yield 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 merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (5)

1. a kind of method of copper catalysis synthesis aromatic hydrocarbons or heterocycle trifluoromethyl ketone, it is characterised in that：It is sub- with cuprous oxide or vulcanization Copper is catalyst, using trifluoroacetone acid alkyl ester and aromatic diazonium salt or heterocycle diazol as raw material, in dimethyl sulfoxide (DMSO) and two The in the mixed solvent of chloromethanes, reacts and aromatic hydrocarbons or heterocycle trifluoromethyl ketone is made；The structural formula of the aromatic diazonium salt is：；The structural formula of the heterocycle diazol is：；Catalyst, aromatic hydrocarbons or heterocycle The molar ratio of diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1-1:0.4-4:0.8-8:1.2-12；Described The volume ratio of the in the mixed solvent of dimethyl sulfoxide (DMSO) and dichloromethane, dimethyl sulfoxide (DMSO) and dichloromethane is：1-3:1-50.
2. the method for a kind of copper catalysis synthesis aromatic hydrocarbons according to claim 1 or heterocycle trifluoromethyl ketone, it is characterised in that： Aromatic moieties in the aromatic diazonium salt structural formula are any one in following formula 1- formulas 25：
；
Heterocyclic moiety in the heterocycle diazol structural formula is any one in following formula 26- formulas 30：
。
3. the method for a kind of copper catalysis synthesis aromatic hydrocarbons according to claim 1 or heterocycle trifluoromethyl ketone, it is characterised in that： The trifluoroacetone acid alkyl ester is trifluoropropyl ketone acid methyl esters or trifluoroacetone acetoacetic ester.
4. the method for a kind of copper catalysis synthesis aromatic hydrocarbons according to claim 1 or heterocycle trifluoromethyl ketone, it is characterised in that： The molar ratio of catalyst, aromatic hydrocarbons or heterocycle diazol, mixed solvent and trifluoroacetone acid alkyl ester is 0.1:0.4:0.8: 1.2。
5. the method for a kind of copper catalysis synthesis aromatic hydrocarbons according to claim 1 or heterocycle trifluoromethyl ketone, it is characterised in that： Comprise the following steps that：In nitrogen atmosphere, catalyst, aromatic hydrocarbons or heterocycle diazonium are added into the container with magnetic stirring apparatus Salt, trifluoroacetone acid alkyl ester and mixed solvent, shut plug after mixing, put it into continue at room temperature stir 1-16 it is small When, extracted with ether, merge organic phase, be washed with distilled water 3 times, organic phase is dried with anhydrous magnesium sulfate, and filtering, then rotates Remove organic solvent；Obtained crude product is eluted by eluant, eluent of pentane by silica gel column chromatography, obtains aromatic hydrocarbons or miscellaneous Ring trifluoromethyl ketone product.
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