CN105503510A - Quinone-catalyzed trifluoromethylation photocatalytic synthesis method - Google Patents
Quinone-catalyzed trifluoromethylation photocatalytic synthesis method Download PDFInfo
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- CN105503510A CN105503510A CN201610003014.8A CN201610003014A CN105503510A CN 105503510 A CN105503510 A CN 105503510A CN 201610003014 A CN201610003014 A CN 201610003014A CN 105503510 A CN105503510 A CN 105503510A
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- trifluoromethylation
- quinone
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- 238000006692 trifluoromethylation reaction Methods 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 150000004053 quinones Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011491 glass wool Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000003814 drug Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ADEBPBSSDYVVLD-UHFFFAOYSA-N donepezil Chemical compound O=C1C=2C=C(OC)C(OC)=CC=2CC1CC(CC1)CCN1CC1=CC=CC=C1 ADEBPBSSDYVVLD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- -1 trichloromethyl compound Chemical class 0.000 description 3
- 208000024827 Alzheimer disease Diseases 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940039856 aricept Drugs 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 150000000644 6-membered heterocyclic compounds Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010026865 Mass Diseases 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a quinone-catalyzed trifluoromethylation photocatalytic synthesis method. According to the method, the using problem of highly-corrosive and highly-toxic fluorinating reagents such as hydrogen fluoride and sulfur tetrafluoride in an existing industrial trifluoromethylation reaction is solved, the heavy metal pollution problem of a catalyst in industry is avoided, and the good actual application prospect is achieved. The metal-free photocatalytic trifluoromethylation reaction is achieved by taking simplest and cheapest benzoquinone and derivatives thereof as a photocatalyst and taking a Langlois reagent-sodium trifluoromethanesulfinate (CF3SO2Na) as a trifluoromethyl source under the mild visible light condition, and a complete full-cycle reaction is achieved through a homemade fixed bed reactor. Trifluoromethyl modification can be further performed on organic molecules with the bioactivity and the pharmaceutical activity according to the actual needs. The method has the advantages that the synthesis condition is mild, the raw materials are cheap and easy to obtain, the environmental pollution is low, large-scale industrial production is facilitated, and the significant economic and social benefit is achieved.
Description
Technical field
The invention belongs to photochemical catalysis technical field of organic synthesis, be specifically related to a kind of trifluoromethyl photocatalysis methodology of organic synthesis of quinone catalysis.
Background technology
In recent years, along with the development of organic fluorine chemistry, fluorinated organic compound obtains investigation and application widely in fields such as medicine, agricultural chemicals, functional materialss.Fluoro-containing group is introduced in drug molecule, its charge distribution can be changed, strengthen its acidity that is fat-soluble and adjacent group, and then strengthen the metabolic stability of medicine, affine bonding force and membrane permeability (M ü ller, K.; Faeh, C.; Diederich, F.Science2007,317,1881-1886).Therefore, the reaction of Development of Novel efficient organic fluorine chemistry, especially trifluoromethylation reaction, the interest of the person that always attracts chemical research for a long time.
A kind of traditional method of industrial trifluoromethylation reaction is the chlorination reaction of first hydrogen on methyl being carried out free radical initiation, and obtain trichloromethyl compound, the fluoridation then exchanged by fluorine chlorine obtains trifluoromethyl compound; Another kind method first acid is prepared into corresponding fluoride compounds, then with HF, acyl fluorides changed into trifluoromethyl (Lv Cuiping, Shen Qilong, Liu Dan, transition metal-catalyzed aromatic compound trifluoromethylation progress [J]. organic chemistry, 2012,32:1380-1387).But two kinds of significant shortcomings of method only have structure comparison to stablize simple toluene analog derivative can bear the strong fluoridation of severe reaction conditions.
Due to metal/d track and σ
c-Fthe interaction of track makes transition metal-catalyzed C-C key form comparatively difficulty, attempts selecting another breakthrough point becoming trifluoromethylation reaction without metal catalyst system.And the ubiquitous quinones of occurring in nature has good oxidation capacity in organic reaction, quinones has extremely strong electronics and hydrogen-taking capacity (Wendlandt, A.E. because it has the chemical structure of conjugation cyclic diketones; Stahl, S.S.Angew.Chem.Int.Ed.2015,54,14638-14658).As long as catalytic specie or the available oxidation capacity of oxygenant are greater than the lowest potential energy (0.6eV) be excited that trifluoromethyl derives negatively charged ion theoretically, just can oxidation conversion trifluoromethanesulpacidc acidc salt.The oxidation potential of the most common monocycle quinones that occurring in nature exists substantially all is greater than 0.71eV, and therefore, quinones is exactly the catalyzer of desirable oxidation trifluoromethylation reaction.And we devise a kind of Manganse Dioxide fixed-bed reactor, effectively overcome the consumption problem of catalyzer in organic reaction, complete the reprocessing cycle of quinones catalyzer.
Therefore, the method researching and developing quinones photochemical catalysis trifluoromethylation reaction organic synthesis under a kind of mild conditions of low cost has important investigation and application and is worth.
Summary of the invention
The object of the present invention is to provide that a kind of system is simple, reaction conditions is gentle, low cost and the photocatalytic synthesis method of the trifluoromethylation product that can prepare in a large number, quasi-solution is determined the high pollution of industrialization trifluoromethylation reaction, high cost problem.Synthesis condition of the present invention is gentle, cheaper starting materials is easy to get, low environment pollutes, be conducive to large-scale industrial production, possesses significant economic and social benefit.
For achieving the above object, the present invention adopts following technical scheme:
A kind of trifluoromethylation photocatalytic synthesis method of quinone catalysis, using monocycle quinones as photocatalyst, Sodium trifluoromethanesulfinate is as trifluoromethyl source, and acetonitrile is as solvent, after substrate mixing, in Manganse Dioxide fixed-bed reactor, carry out building-up reactions.
The mol ratio of monocycle quinones and Sodium trifluoromethanesulfinate is 2:1 ~ 2:7, and the mol ratio of acetonitrile and substrate is 3:1 ~ 3:8.
Described Manganse Dioxide fixed-bed reactor its preparation method is: get 50 ~ 70 order Manganse Dioxide particles and silica dioxide granule is filled in Glass tubing, and two ends sealing, with glass wool, makes Manganse Dioxide fixed-bed reactor.
In described fixed-bed reactor, Manganse Dioxide particle and silica dioxide granule mass ratio are 4:1 ~ 4:11.
The trifluoromethylation photocatalytic synthesis method of described quinone catalysis, concrete steps are:
By monocycle quinones and Sodium trifluoromethanesulfinate mixing, get biased sample in Manganse Dioxide fixed-bed reactor, then pour in reactor by acetonitrile and substrate mixing solutions, reaction is in air atmosphere, carry out under radiation of visible light condition, obtain the Product liquid of homogeneous transparent.
Synthesizing the substrate selected can be the biology/medicine macromolecular cpd of simple aromatic compound, five yuan/6-membered heterocyclic compound and complexity.
Beneficial effect of the present invention is:
(1) the present invention adopts the quinone of environmental protection gentleness to be more the light-catalyzed reaction pattern of catalyzer, only needs simple visible ray illumination just can realize the trifluoromethylation of substrate; The method has that good repeatability, preparation process are simple, low environment pollutes, and is conducive to large-scale industrial production;
(2) catalyzer that the present invention adopts is monocycle quinones organic compound, and avoiding strong acid, the pollution of heavy metal, is whole reaction environmental protection more;
(3) the trifluoromethylation method that the present invention adopts can be used for multiplely having pharmaceutical activity and bioactive substrate, Development volue and having a high potential;
(4) the Manganse Dioxide fixed-bed reactor of the present invention's design effectively overcome quinones consumption in the reaction, improve the utilization ratio of catalyzer widely.
Accompanying drawing explanation
Fig. 1 is the mass spectrum (GC-MS) of primitive reaction of the present invention;
Fig. 2 is the nucleus magnetic resonance of primitive reaction of the present invention
19f collection of illustrative plates (
19fNMR);
Fig. 3 is different quinones electromotive force and the productive rate graph of a relation (electrochemical workstation) of primitive reaction of the present invention;
Fig. 4 is the different light intensity of primitive reaction of the present invention, different wave length and productive rate graph of a relation (light intensity meter, DRS);
Fig. 5 is the mass spectrum (GC-MS) that drug substrate of the present invention is expanded-reacted;
Fig. 6 is the nucleus magnetic resonance that drug substrate of the present invention is expanded-reacted
19f collection of illustrative plates (
19fNMR);
Fig. 7 is fixed-bed reactor photo (containing parameter) of the present invention.
Embodiment
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
Reactions steps of the present invention is as follows:
By monocycle quinones and Sodium trifluoromethanesulfinate mixing, the two mol ratio is 2:1 ~ 2:7; Get biased sample in Manganse Dioxide fixed-bed reactor, then be that the acetonitrile of 3:1 ~ 3:8 and the mixing solutions of substrate are poured in reactor by mol ratio, in air atmosphere, radiation of visible light certain hour, obtains the Product liquid of homogeneous transparent.Separately get Manganse Dioxide particle that 50 ~ 70 orders do not wait and silica dioxide granule is filled in pipe, two kinds of granular masss are than being 4:1 ~ 4:11, and two ends sealing, with glass wool, makes simple Manganse Dioxide fixed-bed reactor.(mass spectrum of Product liquid, as shown in Figure 1, 2, fixed-bed reactor photo as shown in Figure 3 for nuclear magnetic resonance map)
Embodiment 1
Be monocycle quinones (different quinones expansion) and the Sodium trifluoromethanesulfinate mixing of 100:200 by mol ratio; Get biased sample in Manganse Dioxide fixed-bed reactor, then pour in reactor by 15ml acetonitrile and 10ml benzene, in air atmosphere, 800mW radiation of visible light 12h, obtains the Product liquid of homogeneous transparent; (its different quinones records its oxidation potential by electrochemical workstation, and the relation of catalyzer electromotive force and Product yields as shown in Figure 4; The mass spectrum of Product liquid, nuclear magnetic resonance map are as shown in Figure 1, 2).
Embodiment 2
Be benzoquinones and the Sodium trifluoromethanesulfinate mixing of 100:200 by mol ratio; Get biased sample in Manganse Dioxide fixed-bed reactor, then pour in reactor by 15ml acetonitrile and 10ml benzene, in air atmosphere, not etc., the radiation of visible light 10h that optical wavelength 420 ~ 780nm does not wait, does not obtain the Product liquid of homogeneous transparent to light intensity 200-800mW.(it records reaction light intensity by light intensity meter, is recorded the uv-absorbing diffuse reflection spectrum of quinone catalyzer by DRS.The relation of reaction light intensity, reaction wavelength and Product yields as shown in Figure 5; The mass spectrum of Product liquid, nuclear magnetic resonance map are as shown in Figure 1, 2).
Embodiment 3
Be monocycle quinones and the Sodium trifluoromethanesulfinate of 100:200 by mol ratio, mixing; Get biased sample in Manganse Dioxide fixed-bed reactor, again by 15ml acetonitrile and 10ml5,6-dimethoxy-1-indone (Alzheimer's disease medicine (Aricept) medicine presoma) is poured in reactor, in air atmosphere, the radiation of visible light 15h of 800mW different wave length, obtains the Product liquid of homogeneous transparent.(mass spectrum of Product liquid, nuclear magnetic resonance map are as shown in Figure 6,7).
The peak that the GC-MS spectrogram (Fig. 1) of the phenylfluoroform obtained of the present invention's reaction obtains 2.5min is phenylfluoroform after coupling.Repeat equally experiment after by nucleus magnetic resonance,
19the trifluorotoluene peak that 62.68ppm place is standard analyzed by F collection of illustrative plates (Fig. 2).With 5, the trifluoromethylation reaction that 6-dimethoxy-1-indone (Alzheimer's disease medicine (Aricept) medicine presoma) carries out for substrate, we obtain multiple trifluoromethylation product, wherein with 1 substitution product at most (shown in Fig. 6, peak, 15.25min place).Carry out nucleus magnetic resonance after repeating experiment equally, 19F collection of illustrative plates (Fig. 7) analyzes 55.36ppm place for having 1 substitution product of pharmaceutical activity, and 55.88ppm is the by product of other trifluoromethylation.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. the trifluoromethylation photocatalytic synthesis method of a quinone catalysis, it is characterized in that: using monocycle quinones as photocatalyst, Sodium trifluoromethanesulfinate is as trifluoromethyl source, and acetonitrile is as solvent, after substrate mixing, react through visible light catalytic in Manganse Dioxide fixed-bed reactor.
2. the trifluoromethylation photocatalytic synthesis method of quinone catalysis according to claim 1, is characterized in that: the mol ratio of monocycle quinones and Sodium trifluoromethanesulfinate is 2:1 ~ 2:7, and the mol ratio of acetonitrile and substrate is 3:1 ~ 3:8.
3. the trifluoromethylation photocatalytic synthesis method of quinone catalysis according to claim 1, it is characterized in that: described Manganse Dioxide fixed-bed reactor its preparation method is: get 50 ~ 70 order Manganse Dioxide particles and silica dioxide granule is filled in Glass tubing, two ends sealing, with glass wool, makes Manganse Dioxide fixed-bed reactor.
4. the trifluoromethylation photocatalytic synthesis method of quinone catalysis according to claim 3, is characterized in that: in described fixed-bed reactor, Manganse Dioxide particle and silica dioxide granule mass ratio are 4:1 ~ 4:11.
5. the trifluoromethylation photocatalytic synthesis method of quinone catalysis according to claim 1, is characterized in that: concrete steps are:
By monocycle quinones and Sodium trifluoromethanesulfinate mixing, get biased sample in Manganse Dioxide fixed-bed reactor, then pour in reactor by acetonitrile and substrate mixing solutions, reaction is in air atmosphere, carry out under radiation of visible light condition, obtain the Product liquid of homogeneous transparent.
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| CN201610003014.8A CN105503510B (en) | 2016-01-07 | 2016-01-07 | A kind of trifluoromethylation photocatalytic synthesis method of quinone catalysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774121A (en) * | 2018-08-07 | 2018-11-09 | 闽南师范大学 | A kind of method that visible light catalytic prepares alpha-aromatic-β-trifluoromethyl ketone compound |
| CN109092362A (en) * | 2018-07-25 | 2018-12-28 | 大连理工大学 | The organic preparation method and application with polymers of triphenylamine base metal with visible light catalytic heteroaromatic compounds trifluoromethylation performance |
-
2016
- 2016-01-07 CN CN201610003014.8A patent/CN105503510B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| ALISON E. WENDLANDT,ET AL.: "Quinone-Catalyzed Selective Oxidation of Organic Molecules", 《ANGEW.CHEM.INT.ED.》 * |
| DALE J. WILGER，ET AL.: "Catalytic hydrotrifluoromethylation of styrenes and unactivated aliphatic alkenes via an organic photoredox system", 《CHEM. SCI.》 * |
| LEI CUI，ET AL.: "Metal-Free Direct C-H Perfluoroalkylation of Arenes and Heteroarenes Using a Photoredox Organocatalyst", 《ADVANCED SYNTHESIS CATALYSIS》 * |
| 曹晓慧: "醋酸锰引发的三氟甲基自由基的选择性反应研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092362A (en) * | 2018-07-25 | 2018-12-28 | 大连理工大学 | The organic preparation method and application with polymers of triphenylamine base metal with visible light catalytic heteroaromatic compounds trifluoromethylation performance |
| CN109092362B (en) * | 2018-07-25 | 2021-07-06 | 大连理工大学 | Preparation method and application of triphenylamine-based metal organic coordination polymer with visible light catalytic aromatic heterocyclic compound trifluoromethyl performance |
| CN108774121A (en) * | 2018-08-07 | 2018-11-09 | 闽南师范大学 | A kind of method that visible light catalytic prepares alpha-aromatic-β-trifluoromethyl ketone compound |
| CN108774121B (en) * | 2018-08-07 | 2021-09-10 | 闽南师范大学 | Method for preparing alpha-aryl-beta-trifluoromethyl ketone compound by visible light catalysis |
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