CN108002991A - A kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst - Google Patents
A kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst Download PDFInfo
- Publication number
- CN108002991A CN108002991A CN201711385186.7A CN201711385186A CN108002991A CN 108002991 A CN108002991 A CN 108002991A CN 201711385186 A CN201711385186 A CN 201711385186A CN 108002991 A CN108002991 A CN 108002991A
- Authority
- CN
- China
- Prior art keywords
- halogenated aryl
- reaction
- aryl hydrocarbon
- visible light
- light catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
-
- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- 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 kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst, belong to visible light catalytic technical field of organic synthesis.Comprise the following steps:1) weigh halogenated aryl hydrocarbon to be placed in reaction vessel, add solvent;2) inflated with nitrogen deoxygenation 0~50 minute into reaction vessel, adds alkali during deoxygenation;3) reaction vessel is sealed, is positioned over above wavelength is 400~500nm, power is 0.5~30W light emitting diode and is irradiated, be stirred at room temperature reaction 3~48 it is small when, reaction terminates.Without using photoredox catalyst expensive or that synthesis is complicated reaction, and reaction substrate wide adaptability can be achieved, reaction yield is high in this method under room temperature and temperate condition.
Description
Technical field
The invention belongs to visible light catalytic technical field of organic synthesis, and in particular to one kind is without photoredox catalyst
Visible light catalytic halogenated aryl hydrocarbon dehalogenation method.
Background technology
Develop feasible visible light catalytic method and probe into the magnificent mission that science reason therein is chemist.Preferably
Visible light catalytic method needs to have the following conditions:Reaction efficiency is high, substrate wide adaptability and functional group selectivity are good.Separately
Outside, from the perspective of industrial-scale production, the method developed should also meet that easily operated grade low with production cost is special
Point;Meanwhile also to avoid using expensive or chemical synthesis step complexity photoredox catalyst as far as possible.
In recent years, scientists have developed a series of visible light catalytic reaction systems, and many organic molecules are all used as can
See the substrate of light-catalyzed reaction.Halogenated aryl hydrocarbon, as most substrates is applied in metal catalytic C-C coupling reaction, visible
Photocatalysis field also has received widespread attention.In fact, before more than 50 years, the dehalogenation reaction of halogenated aryl hydrocarbon has just attracted crowd
The research interest of more chemists.However, in method used at that time, it is required for using the ultraviolet source of high-energy.These light sources
On the one hand consume energy high, height is required to consersion unit, reaction safety also decreases.So as to reduce it and realize commercial Application
Possibility.Since 2014, the light-catalyzed reaction based on halogenated aryl hydrocarbon makes great progress, wherein being the most significantly
Ultraviolet source is instead of using visible light source, so as to effectively reduce energy consumption of reaction and security, is established to go further to apply
Solid foundation is determined.But, it is seen that the introducing of light also brings the problem of new, it has been reported that using halogenated aryl hydrocarbon as reaction bottom
In the visible light catalytic reaction of thing (including dehalogenation and carbon-to-carbon coupling), wherein must all use precious metals complex or photosensitive
Agent is as photoredox catalyst.These photoredox catalyst often there are expensive or synthesis it is complicated the problems such as,
More importantly the introducing of photoredox catalyst can increase the operation difficulty of follow-up separating-purifying, so as to influence the reality of reaction
Border yield.Therefore, visible light catalytic dehalogenation and the carbon-to-carbon coupling without halogenated aryl hydrocarbon under photoredox catalysts conditions are developed
Reaction technology tool is of great significance.
The content of the invention
It is an object of the invention to provide a kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation without photoredox catalyst
Method, this method are under room temperature and temperate condition without using photoredox catalyst expensive or that synthesis is complicated
The dehalogenation of halogenated aryl hydrocarbon can be achieved.
The present invention is to be achieved through the following technical solutions:
The invention discloses a kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst, including
Following steps:
1) weigh halogenated aryl hydrocarbon to be placed in reaction vessel, add solvent;
2) inflated with nitrogen deoxygenation 0~50 minute into reaction vessel, adds alkali during deoxygenation;
3) reaction vessel is sealed, be positioned over wavelength be 400~500nm, power be on the light emitting diode of 0.5~30W
Side be irradiated, be stirred at room temperature reaction 3~48 it is small when, reaction terminates.
Preferably, halogenated aryl hydrocarbon, alkali, the dosage molar ratio of solvent are 1:(0.1~10):(30~200).
Preferably, in step 1) halogenated aryl hydrocarbon be to Iodoacetophenone, parabromoacetophenone, parachloroacetophenone, to methyl iodobenzene,
Between benzaldehyde iodine, p-bromobenzaldehyde, o-bromobenzaldehye, to benzaldehyde iodine, adjacent iodobenzene acetonitrile, to iodobenzene acetonitrile, an iodobenzene acetonitrile,
Bromophenyl acetonitrile, a bromobenzylcyanide, adjacent chlorobenzene acetonitrile, a chlorobenzene acetonitrile, 4-Iodobenzoic acid methyl esters or the chloro- 4- trifluoromethyls of 2-
Pyridine.
Preferably, solvent is toluene, tetrahydrofuran, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane, two sulphur in step 1)
Sulfoxide or acetonitrile.
Preferably, alkali is triethylamine, propylamine, potassium tert-butoxide, sodium acetate or sodium hydroxide in step 2).
Preferably, alkali and pyrroles or azole derivatives are sequentially added in step 2) during deoxygenation.
It is further preferred that halogenated aryl hydrocarbon, alkali, pyrroles or azole derivatives, the dosage molar ratio of solvent are 1:
(0.1~10):(1~45):(30~200).
It is further preferred that azole derivatives are N- methylpyrroles or N- phenylpyrroles in step 2).
It is further preferred that reaction end is further included using petroleum ether and ethyl acetate as eluent progress column in step 3)
Chromatographic isolation, through vacuum drying post processing at 30~60 DEG C.
It is further preferred that the volume ratio of petroleum ether and ethyl acetate is (10:1)~(50:1).
Compared with prior art, the present invention has technique effect beneficial below:
A kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst disclosed by the invention, in alkali
Property under the conditions of, LED light of the selection with suitable wavelength and power as light source, due to the introducing of halogen often increase be between alter
More and promote the generation of triplet state, so some molecules for containing halogen are widely used as Triplet Sensitizers.Different excitation state
The architectural difference of lower carbon-halogen bond (C-X) is very big, its singlet excited state structure is similar to ground state, swashs however, working as in triplet state
When sending out state, the bond distance of C-X can substantially increase, this also means that its bond energy can significantly weaken, basis is provided for further fracture.Separately
Outside, halogen key is a kind of noncovalent interaction being widely present between halogen atom and lewis base, moreover, in suitable condition
Under, the presence of halogen key can promote the generation of C-X triplet states and contribute to it to be stabilized.Therefore, the present invention utilizes lewis base
Halogen bond effect between halogenated aryl hydrocarbon, under visible light illumination, that is, select in alkaline conditions, selection have suitable wavelength and
The LED light of power makes the C-X in halogenated aryl hydrocarbon reach triplet state and by advanced activation to being broken, so as to be had as light source
There is the aryl radical of high reaction activity, can effectively realize the dehalogenation of halogenated aryl hydrocarbon.And this method is easy to operate, without making
With photoredox catalyst expensive or that synthesis is complicated, cost is low, and raw material is easy to get, and reaction condition is gentle, and energy consumption is low, instead
Should be efficient, it is low for equipment requirements, it is the efficient means for realizing halogenated aryl hydrocarbon degraded, in the industrial production with wide application
Prospect.
Further by sequentially adding alkali and pyrroles or azole derivatives during deoxygenation, so as to effectively realize visible
It is photocatalysis, even without the carbon-to-carbon between the halogenated aryl hydrocarbon and pyrroles or azole derivatives under photoredox catalysts conditions
Connection reaction.
Brief description of the drawings
Fig. 1 is the dehalogenation method schematic diagram of the present invention;
Fig. 2 is the gas chromatography mass spectrometry characterization result of iodo aromatic hydrocarbon dehalogenation reaction;
Fig. 3 is the gas chromatography mass spectrometry characterization result of aryl bromide dehalogenation reaction;
Fig. 4 is the gas chromatography mass spectrometry characterization result of halogenated aryl hydrocarbon dehalogenation reaction;
Fig. 5 is the nucleus magnetic hydrogen spectrum of compound 1a;The nuclear-magnetism carbon that Fig. 6 is compound 1a is composed;
Fig. 7 is the nucleus magnetic hydrogen spectrum of compound 1b;The nuclear-magnetism carbon that Fig. 8 is compound 1b is composed;
Fig. 9 is the nucleus magnetic hydrogen spectrum of compound 1c;The nuclear-magnetism carbon that Figure 10 is compound 1c is composed;
Figure 11 is the nucleus magnetic hydrogen spectrum of compound 2a;The nuclear-magnetism carbon that Figure 12 is compound 2a is composed;
Figure 13 is the nucleus magnetic hydrogen spectrum of compound 2b;Figure 14 is the nucleus magnetic hydrogen spectrum of compound 2c;
The nuclear-magnetism carbon that Figure 15 is compound 2c is composed;Figure 16 is the nucleus magnetic hydrogen spectrum of compound 3a;
The nuclear-magnetism carbon that Figure 17 is compound 3a is composed;Figure 18 is the nucleus magnetic hydrogen spectrum of compound 3b;
The nuclear-magnetism carbon that Figure 19 is compound 3b is composed;Figure 20 is the nucleus magnetic hydrogen spectrum of compound 3c;
The nuclear-magnetism carbon that Figure 21 is compound 3c is composed;Figure 22 is the nucleus magnetic hydrogen spectrum of compound 4a;
The nuclear-magnetism carbon that Figure 23 is compound 4a is composed;Figure 24 is the nucleus magnetic hydrogen spectrum of compound 4b;
The nuclear-magnetism carbon that Figure 25 is compound 4b is composed;Figure 26 is the nucleus magnetic hydrogen spectrum of compound 4c;
The nuclear-magnetism carbon that Figure 27 is compound 4c is composed;Figure 28 is the nucleus magnetic hydrogen spectrum of compound 5a;
The nuclear-magnetism carbon that Figure 29 is compound 5a is composed;Figure 30 is the nucleus magnetic hydrogen spectrum of compound 5b;
The nuclear-magnetism carbon that Figure 31 is compound 5b is composed;Figure 32 is the nucleus magnetic hydrogen spectrum of compound 5c;
The nuclear-magnetism carbon that Figure 33 is compound 5c is composed;Figure 34 is the nucleus magnetic hydrogen spectrum of compound 6a;
The nuclear-magnetism carbon that Figure 35 is compound 6a is composed;Figure 36 is the nucleus magnetic hydrogen spectrum of compound 6b;
The nuclear-magnetism carbon that Figure 37 is compound 6b is composed;Figure 38 is the nucleus magnetic hydrogen spectrum of compound 6c;
The nuclear-magnetism carbon that Figure 39 is compound 6c is composed.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The invention discloses a kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst, it is related to
C-C coupling reaction between the dehalogenation reaction and halogenated aryl hydrocarbon and pyrroles or azole derivatives of halogenated aryl hydrocarbon, such as Fig. 1 institutes
Show.
First, the dehalogenation reaction of halogenated aryl hydrocarbon
Embodiment 1 weighs 0.05mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 20 minutes, adds 30 μ L triethylamines during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be
Be irradiated above the light emitting diode (LED) of 2W, be stirred at room temperature reaction 24 it is small when.Afterwards, gas chromatography-mass spectrography is utilized
Characterized by techniques dehalogenation reaction yield, the yield of acetophenone is 83.4%, and gas chromatography mass spectrometry characterization result is as shown in Figure 2;Wherein halo
Aromatic hydrocarbons is Iodoacetophenone, and solvent is toluene.
Embodiment 2 weighs 0.02mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 1mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 10 minutes, adds 15 μ L triethylamines during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be
Be irradiated above the light emitting diode (LED) of 0.5W, be stirred at room temperature reaction 12 it is small when.Afterwards, gas chromatography-mass spectrometry is utilized
With characterized by techniques dehalogenation reaction yield, the yield of adjacent benzene acetonitrile is 80.7%, and gas chromatography mass spectrometry characterization result is as shown in fig. 2;Wherein
Halogenated aryl hydrocarbon is adjacent iodobenzene acetonitrile, and solvent is tetrahydrofuran.
Embodiment 3 weighs 0.1mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, inflated with nitrogen removes into reaction bulb
Oxygen 25 minutes, adds 30 μ L potassium tert-butoxides during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 450nm, power be
Be irradiated above the light emitting diode (LED) of 30W, be stirred at room temperature reaction 18 it is small when.Afterwards, gas chromatography-mass spectrometry is utilized
With characterized by techniques dehalogenation reaction yield, the yield of benzaldehyde is 51.5%, and gas chromatography mass spectrometry characterization result is as shown in Figure 2;Wherein halogen
It is that solvent is n,N-Dimethylformamide to benzaldehyde iodine for aromatic hydrocarbons.
Embodiment 4 weighs 0.2mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 3mL solvents, inflated with nitrogen removes into reaction bulb
Oxygen 15 minutes, adds 50 μ L sodium acetates during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 480nm, power 20W
Light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 30 it is small when.Afterwards, gas chromatography-mass spectrography skill is utilized
Art characterizes dehalogenation reaction yield, and the yield to methylbenzene is 44.6%, and gas chromatography mass spectrometry characterization result is as shown in Figure 2;Wherein halo
Aromatic hydrocarbons is that solvent is Isosorbide-5-Nitrae-dioxane to methyl iodobenzene.
Embodiment 5 weighs 0.8mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 5mL solvents, inflated with nitrogen removes into reaction bulb
Oxygen 50 minutes, adds 300 μ L sodium hydroxides during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be
Be irradiated above the light emitting diode (LED) of 30W, be stirred at room temperature reaction 48 it is small when.Afterwards, gas chromatography-mass spectrometry is utilized
With characterized by techniques dehalogenation reaction yield, the yield to acetophenone is 82.0%, and gas chromatography mass spectrometry characterization result is as shown in Figure 3;Wherein
Halogenated aryl hydrocarbon is parabromoacetophenone, and solvent is two sulphur sulfoxides.
Embodiment 6 weighs 0.2mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 5mL solvents, inflated with nitrogen removes into reaction bulb
Oxygen 25 minutes, adds 200 μ L triethylamines during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be
Be irradiated above the light emitting diode (LED) of 25W, be stirred at room temperature reaction 3 it is small when.Afterwards, gas chromatography-mass spectrography is utilized
Characterized by techniques dehalogenation reaction yield, the yield to benzaldehyde is 76.1%, and gas chromatography mass spectrometry characterization result is as shown in Figure 3;Wherein halogen
It is p-bromobenzaldehyde for aromatic hydrocarbons, solvent is acetonitrile.
Embodiment 7 weighs 1mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 3mL solvents, the inflated with nitrogen deoxygenation into reaction bulb
15 minutes, 50 μ L triethylamines are added during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be 30W's
Be irradiated above light emitting diode (LED), be stirred at room temperature reaction 48 it is small when.Afterwards, Gas chromatographyMass spectrometry is utilized
Characterization dehalogenation reaction yield, the yield 47.9% of adjacent benzaldehyde, gas chromatography mass spectrometry characterization result are as shown in Figure 3;Wherein halogenated aryl hydrocarbon
For o-bromobenzaldehye, solvent is n,N-Dimethylformamide.
Embodiment 8 weighs 0.01mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 35 minutes, adds 60 μ L triethylamines during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power be
Be irradiated above the light emitting diode (LED) of 1W, be stirred at room temperature reaction 5 it is small when.Afterwards, gas chromatography-mass spectrography is utilized
Characterized by techniques dehalogenation reaction yield, the yield to acetophenone is 66.2%, and gas chromatography mass spectrometry characterization result is as shown in Figure 4;Wherein halogen
It is parachloroacetophenone for aromatic hydrocarbons, solvent is two sulphur sulfoxides.
Embodiment 9 weighs 0.5mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 3mL solvents, inflated with nitrogen removes into reaction bulb
Oxygen 35 minutes, adds 60 μ L triethylamines during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 400nm, power 1W
Light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 10 it is small when.Afterwards, gas chromatography-mass spectrography skill is utilized
Art characterizes dehalogenation reaction yield, and the yield of 4- trifluoromethyl pyridines is 67.0%, and gas chromatography mass spectrometry characterization result is as shown in Figure 4;Its
Middle halogenated aryl hydrocarbon is the chloro- 4- trifluoromethyl pyridines of 2-, and solvent is toluene.
Embodiment 10 weighs 0.5mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 30 minutes, adds 50 μ L propylamine during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over wavelength be 500nm, power 25W
Light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 15 it is small when.Afterwards, gas chromatography-mass spectrography skill is utilized
Art characterizes dehalogenation reaction yield, and the yield of 4- trifluoromethyl pyridines is 68%, and gas chromatography mass spectrometry characterization result is as shown in Figure 4;Wherein
Halogenated aryl hydrocarbon is the chloro- 4- trifluoromethyl pyridines of 2-, and solvent is tetrahydrofuran.
2nd, the C-C coupling reaction between halogenated aryl hydrocarbon and pyrroles or azole derivatives
Embodiment 11 weighs 0.1mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 20 minutes, adds 30 μ L triethylamines and 2mM pyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, being positioned over wavelength is
400nm, power be 2W light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 24 it is small when.After reaction, close
Light source, reaction mixture are spin-dried for, and are carried out pillar layer separation as eluent using petroleum ether and ethyl acetate, are done through vacuum at 40 DEG C
Dry, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 1a, compound 1a are composed respectively as shown in Figure 5 and Figure 6, compound
The yield of 1a is 90%, as shown in table 1;Wherein halogenated aryl hydrocarbon is that solvent is toluene to Iodoacetophenone.Pyrroles in embodiment 11
When replacing with N- methylpyrroles, nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum of carbon-to-carbon coupled product 1b, compound 1b are obtained respectively such as Fig. 7
Shown in Fig. 8, the yield of compound 1b is 85%, as shown in table 1.When the pyrroles in embodiment 11 replaces with N- phenylpyrroles
When, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon that obtain carbon-to-carbon coupled product 1c, compound 1c are composed respectively as shown in Figure 9 and Figure 10, compound
The yield of 1c is 55%, as shown in table 1.
1 various halogenated aryl hydrocarbons of table and the yield list of azole derivatives reaction
X=I, Br, ClR=H, Me, Ph
Embodiment 12 weighs 0.3mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 3mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 30 minutes, adds 50 μ L triethylamines and 6mM pyrroles, afterwards, reaction vessel is sealed, being positioned over wavelength is successively during deoxygenation
420nm, power be 20W light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 36 it is small when.After reaction, close
Light source, reaction mixture are spin-dried for, and are carried out pillar layer separation as eluent using petroleum ether and ethyl acetate, are done through vacuum at 50 DEG C
Dry, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 2a, compound 2a are composed respectively as is illustrated by figs. 11 and 12, chemical combination
The yield of thing 2a is 93%, as shown in table 1;Wherein halogenated aryl hydrocarbon is 4-Iodobenzoic acid methyl esters, and solvent is tetrahydrofuran.Work as implementation
When pyrroles in example 12 replaces with N- methylpyrroles, nucleus magnetic hydrogen spectrum such as Figure 13 institutes of carbon-to-carbon coupled product 2b, compound 2b are obtained
Show, the yield of compound 2b is 91%, as shown in table 1.When the pyrroles in embodiment 12 replaces with N- phenylpyrroles, obtain
The nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon of carbon-to-carbon coupled product 2c, compound 2c are composed respectively as shown in Figure 14 and Figure 15, the production of compound 2c
Rate is 60%, as shown in table 1.
Embodiment 13 weighs 0.5mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 4mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 50 minutes, adds 100 μ L triethylamines and 2mM N- phenylpyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, placed
Be irradiated above wavelength is 500nm, power is 30W light emitting diode (LED), be stirred at room temperature reaction 48 it is small when.Reaction
After, light source is closed, reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, through 40 DEG C
Lower vacuum drying, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 3a, compound 3a are composed as shown in Figure 16 and Figure 17,
The yield of compound 3a is 88%, as shown in table 1;Wherein halogenated aryl hydrocarbon is to benzaldehyde iodine, solvent N, N- dimethyl formyl
Amine.When the pyrroles in embodiment 13 replaces with N- methylpyrroles, the nuclear-magnetism hydrogen of carbon-to-carbon coupled product 3b, compound 3b is obtained
As shown in Figures 18 and 19, the yield of compound 3b is 85%, as shown in table 1 for spectrum and nuclear-magnetism carbon spectrum.Pyrroles in embodiment 13
When replacing with N- phenylpyrroles, nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum such as Figure 20 and figure of carbon-to-carbon coupled product 3c, compound 3c are obtained
Shown in 21, the yield of compound 3c is 53%, as shown in table 1.
Embodiment 14 weighs 0.1mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 0 minute, adds 30 μ L triethylamines and 5mM pyrroles or derivatives thereof successively during deoxygenation.Afterwards, reaction vessel is sealed, put
Be placed in above wavelength is 420nm, power is 20W light emitting diode (LED) and be irradiated, be stirred at room temperature reaction 20 it is small when.Instead
After answering, light source is closed, reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, through 30
It is dried in vacuo at DEG C, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 4a, compound 4a are composed such as Figure 22 and Figure 23 institutes
Show, the yield of compound 4a is 95%, as shown in table 1;Wherein halogenated aryl hydrocarbon is that solvent is Isosorbide-5-Nitrae-dioxy six to iodobenzene acetonitrile
Ring.When the pyrroles in embodiment 14 replaces with N- methylpyrroles, the nuclear-magnetism hydrogen of carbon-to-carbon coupled product 4b, compound 4b is obtained
As shown in figures 24 and 25, compound 4b yields are 93%, as shown in table 1 for spectrum and nuclear-magnetism carbon spectrum.Pyrroles in embodiment 14
When replacing with N- phenylpyrroles, nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum such as Figure 26 and figure of carbon-to-carbon coupled product 4c, compound 4c are obtained
Shown in 27, the yield of compound 4c is 63%, as shown in table 1.
Embodiment 15 weighs 0.9mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 5mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 40 minutes, adds 600 μ L triethylamines and 30mM pyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, is positioned over wavelength
Be irradiated above the light emitting diode for being 30W for 420nm, power (LED), be stirred at room temperature reaction 30 it is small when.After reaction,
Light source is closed, reaction mixture is spin-dried for, and is carried out pillar layer separation as eluent using petroleum ether and ethyl acetate, is done through vacuum at 40 DEG C
Dry, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 5a, compound 5a are composed as shown in Figure 28 and Figure 29, compound 5a
Yield be 86%, as shown in table 1;Wherein halogenated aryl hydrocarbon be between iodobenzene acetonitrile, solvent is two sulphur sulfoxides.When in embodiment 15
When pyrroles replaces with N- methylpyrroles, nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum such as Figure 30 of carbon-to-carbon coupled product 5b, compound 5b are obtained
Shown in Figure 31, the yield of compound 5b is 83%, as shown in table 1.When the pyrroles in embodiment 15 replaces with N- phenylpyrroles
When, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon that obtain carbon-to-carbon coupled product 5c, compound 5c are composed as shown in Figure 32 and Figure 33, compound 5c
Yield be 59%, as shown in table 1.
Embodiment 16 weighs 0.6mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 4mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 30 minutes, adds 150 μ L triethylamines and 24mM pyrroles or derivatives thereof successively during deoxygenation.Afterwards, reaction vessel is sealed,
Be positioned over above wavelength is 450nm, power is 30W light emitting diode (LED) and be irradiated, be stirred at room temperature reaction 20 it is small when.
After reaction, light source is closed, reaction mixture is spin-dried for, and pillar layer separation, warp are carried out as eluent using petroleum ether and ethyl acetate
It is dried in vacuo at 35 DEG C, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon for obtaining carbon-to-carbon coupled product 6a, compound 6a are composed such as Figure 34 and Figure 35 institutes
Show, the yield of compound 6a is 96%, as shown in table 1;Wherein halogenated aryl hydrocarbon is adjacent iodobenzene acetonitrile, and solvent is acetonitrile.Work as implementation
When pyrroles in example 16 replaces with N- methylpyrroles, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon of carbon-to-carbon coupled product 6b, compound 6b is obtained
Spectrum is as shown in Figure 36 and Figure 37, and the yield of compound 6b is 96%, as shown in table 1.When the pyrroles in embodiment 16 replaces with N-
During phenylpyrrole, the nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon that obtain carbon-to-carbon coupled product 6c, compound 6c are composed as shown in Figure 38 and Figure 39,
The yield of compound 6c is 58%, as shown in table 1.
Embodiment 17 weighs 0.3mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 2mL solvents, the inflated with nitrogen into reaction bulb
Deoxygenation 15 minutes, adds 60 μ L sodium hydroxides and 18mM pyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, is positioned over ripple
A length of 420nm, power be 30W light emitting diode (LED) above be irradiated, be stirred at room temperature reaction 14 it is small when.Reaction terminates
Afterwards, light source is closed, reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, through true at 40 DEG C
Sky is dry, and the yield for obtaining carbon-to-carbon coupled product 7a, compound 7a is 86%, as shown in table 1;Wherein halogenated aryl hydrocarbon is adjacent bromine
Benzene acetonitrile, solvent are n,N-Dimethylformamide.When the pyrroles in embodiment 17 replaces with N- methylpyrroles, carbon-to-carbon is obtained
The yield of coupled product 7b, compound 7b are 88%, as shown in table 1.When the pyrroles in embodiment 17 replaces with N- phenylpyrroles
When, the yield for obtaining carbon-to-carbon coupled product 7c, compound 7c is 49%, as shown in table 1.
Embodiment 18 weighs 0.05mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 1.5mL solvents, the nitrogen charging into reaction bulb
Gas deoxygenation 30 minutes, adds 60 μ L sodium acetates and 32mM pyrroles or derivatives thereof successively during deoxygenation.Afterwards, it is reaction vessel is close
Envelope, is positioned over above the light emitting diode (LED) that wavelength is 400nm, power is 0.5W and is irradiated, it is small that reaction 3 is stirred at room temperature
When.After reaction, light source is closed, reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate,
Through being dried in vacuo at 30 DEG C, the yield for obtaining carbon-to-carbon coupled product 8a, compound 8a is 90%, as shown in table 1;Wherein halo
Aromatic hydrocarbons be between bromobenzylcyanide, solvent is two sulphur sulfoxides.When the pyrroles in embodiment 18 replaces with N- methylpyrroles, obtain carbon-
The yield of carbon coupled product 8b, compound 8b are 88%, as shown in table 1.When the pyrroles in embodiment 18 replaces with N- phenyl pyrazolines
When coughing up, the yield for obtaining carbon-to-carbon coupled product 8c, compound 8c is 53%, as shown in table 1.
Embodiment 19 weighs 0.05mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 1.5mL solvents, the nitrogen charging into reaction bulb
Gas deoxygenation 30 minutes, adds 60 μ L propylamine and 32mM N- methylpyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, placed
Be irradiated above wavelength is 400nm, power is 0.5W light emitting diode (LED), be stirred at room temperature reaction 3 it is small when.Reaction
After, light source is closed, reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, through 30 DEG C
Lower vacuum drying, the yield for obtaining carbon-to-carbon coupled product 9a, compound 9a are 93%, as shown in table 1;Wherein halogenated aryl hydrocarbon is
Adjacent chlorobenzene acetonitrile, solvent are toluene.When the pyrroles in embodiment 19 replaces with N- methylpyrroles, carbon-to-carbon coupled product is obtained
The yield of 9b, compound 9b are 90%, as shown in table 1.When the pyrroles in embodiment 19 replaces with N- phenylpyrroles, obtain
The yield of carbon-to-carbon coupled product 9c, compound 9c are 52%, as shown in table 1.
Embodiment 20 weighs 0.05mM halogenated aryl hydrocarbons in reaction bulb, adds solvent 1.5mL solvents, the nitrogen charging into reaction bulb
Gas deoxygenation 30 minutes, adds 60 μ L potassium tert-butoxides and 32mM pyrroles successively during deoxygenation.Afterwards, reaction vessel is sealed, be positioned over
Be irradiated above wavelength is 400nm, power is 0.5W light emitting diode (LED), be stirred at room temperature reaction 3 it is small when.Reaction knot
Shu Hou, closes light source, and reaction mixture is spin-dried for, and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, through at 60 DEG C
Vacuum drying, the yield for obtaining carbon-to-carbon coupled product 10a, compound 10a are 83%, as shown in table 1;Wherein halogenated aryl hydrocarbon is
Between chlorobenzene acetonitrile, solvent is tetrahydrofuran.When the pyrroles in embodiment 20 replaces with N- methylpyrroles, carbon-to-carbon coupling is obtained
The yield of product 10b, compound 10b are 76%, as shown in table 1.When the pyrroles in embodiment 20 replaces with N- phenylpyrroles,
The yield for obtaining carbon-to-carbon coupled product 10c, compound 10c is 49%, as shown in table 1.
A kind of in conclusion visible light catalytic halogenated aryl hydrocarbon dehalogenation without photoredox catalyst disclosed by the invention
Method (C-C coupling reaction between the dehalogenation and halogenated aryl hydrocarbon and pyrroles or azole derivatives of halogenated aryl hydrocarbon), without making
With photoredox catalyst expensive or that synthesis is complicated, a variety of halogenated aryl hydrocarbons can be achieved under room temperature and temperate condition
Dehalogenation and halogenated aryl hydrocarbon and pyrroles or azole derivatives between C-C coupling reaction.Meanwhile the reaction substrate adaptability
Extensively, reaction system is simple, and last handling process is simple, and reaction yield is high, and practicality is high.In addition, it can be obtained using the method
A series of compounds having great application prospect in functional molecular or biomedicine field.
Claims (10)
- A kind of 1. visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst, it is characterised in that including with Lower step:1) weigh halogenated aryl hydrocarbon to be placed in reaction vessel, add solvent;2) inflated with nitrogen deoxygenation 0~50 minute into reaction vessel, and alkali is added during deoxygenation;3) reaction vessel is sealed, be positioned over above wavelength is 400~500nm, power is 0.5~30W light emitting diode into Row irradiation, be stirred at room temperature reaction 3~48 it is small when, reaction terminates.
- 2. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 1 without photoredox catalyst, its It is characterized in that, the dosage molar ratio of halogenated aryl hydrocarbon, alkali and solvent is 1:(0.1~10):(30~200).
- 3. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 1 without photoredox catalyst, its Be characterized in that, in step 1) halogenated aryl hydrocarbon be to Iodoacetophenone, parabromoacetophenone, parachloroacetophenone, to methyl iodobenzene, an iodobenzene Formaldehyde, p-bromobenzaldehyde, o-bromobenzaldehye, to benzaldehyde iodine, adjacent iodobenzene acetonitrile, to iodobenzene acetonitrile, iodobenzene acetonitrile, bromophenyl Acetonitrile, a bromobenzylcyanide, adjacent chlorobenzene acetonitrile, a chlorobenzene acetonitrile, 4-Iodobenzoic acid methyl esters or the chloro- 4- trifluoromethyl pyridines of 2-.
- 4. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 1 without photoredox catalyst, its Be characterized in that, in step 1) solvent for toluene, tetrahydrofuran, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane, two sulphur sulfoxides or Person's acetonitrile.
- 5. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 1 without photoredox catalyst, its It is characterized in that, alkali is triethylamine, propylamine, potassium tert-butoxide, sodium acetate or sodium hydroxide in step 2).
- 6. taken off according to visible light catalytic halogenated aryl hydrocarbon of the Claims 1 to 5 any one of them without photoredox catalyst Halogen method, it is characterised in that alkali and pyrroles or azole derivatives are sequentially added during the deoxygenation described in step 2).
- 7. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 6 without photoredox catalyst, its It is characterized in that, the dosage molar ratio of halogenated aryl hydrocarbon, alkali, pyrroles or azole derivatives and solvent is 1:(0.1~10):(1~45): (30~200).
- 8. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst according to claim 6 or 7, It is characterized in that, azole derivatives are N- methylpyrroles or N- phenylpyrroles in step 2).
- 9. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 6 without photoredox catalyst, its It is characterized in that, is further included after reaction in step 3) and pillar layer separation is carried out as eluent using petroleum ether and ethyl acetate, so By vacuum drying post-processing operation at 30~60 DEG C.
- 10. the visible light catalytic halogenated aryl hydrocarbon dehalogenation method according to claim 9 without photoredox catalyst, its It is characterized in that, the volume ratio of petroleum ether and ethyl acetate is (10:1)~(50:1).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711385186.7A CN108002991B (en) | 2017-12-20 | 2017-12-20 | Visible light catalytic halogenated aromatic hydrocarbon dehalogenation method without photooxidation-reduction catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711385186.7A CN108002991B (en) | 2017-12-20 | 2017-12-20 | Visible light catalytic halogenated aromatic hydrocarbon dehalogenation method without photooxidation-reduction catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108002991A true CN108002991A (en) | 2018-05-08 |
CN108002991B CN108002991B (en) | 2021-01-05 |
Family
ID=62060231
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711385186.7A Active CN108002991B (en) | 2017-12-20 | 2017-12-20 | Visible light catalytic halogenated aromatic hydrocarbon dehalogenation method without photooxidation-reduction catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108002991B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109336756A (en) * | 2018-11-20 | 2019-02-15 | 河南大学 | A kind of hydrogenation-dehalogenation method of halogenated aromatic |
CN110818532A (en) * | 2019-10-18 | 2020-02-21 | 温州大学 | Method for preparing phenol and derivatives thereof by photocatalysis of metal-free halogenated aromatic hydrocarbon |
CN112138718A (en) * | 2019-06-26 | 2020-12-29 | 北京工商大学 | Method for synthesizing biaryl compound by coupling covalent organic framework material photocatalysis C-C bond |
CN112724002A (en) * | 2020-12-31 | 2021-04-30 | 江汉大学 | Method for selectively reducing bromoacetophenone by alkali regulation and control and application |
CN114105746A (en) * | 2021-11-24 | 2022-03-01 | 温州大学 | Reduction dehalogenation method of photocatalysis alpha-halogenated carbonyl compound |
CN116102605A (en) * | 2023-01-18 | 2023-05-12 | 奥锐特药业股份有限公司 | Dehalogenation method of 9-halogenated steroid compound |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1403428A (en) * | 2002-09-11 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalytic hydrogenation and dehalogenation process of phenoxy phenol halide compound |
CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
-
2017
- 2017-12-20 CN CN201711385186.7A patent/CN108002991B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1403428A (en) * | 2002-09-11 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalytic hydrogenation and dehalogenation process of phenoxy phenol halide compound |
CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
Non-Patent Citations (1)
Title |
---|
M. OBST等: "Solvent-free coupling of aryl halides with pyrroles applying visible-light photocatalysis", 《REACT.CHEM.ENG.》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109336756A (en) * | 2018-11-20 | 2019-02-15 | 河南大学 | A kind of hydrogenation-dehalogenation method of halogenated aromatic |
CN109336756B (en) * | 2018-11-20 | 2021-05-11 | 河南大学 | Hydrogenation dehalogenation method of halogenated aromatic hydrocarbon |
CN112138718A (en) * | 2019-06-26 | 2020-12-29 | 北京工商大学 | Method for synthesizing biaryl compound by coupling covalent organic framework material photocatalysis C-C bond |
CN112138718B (en) * | 2019-06-26 | 2023-06-16 | 北京工商大学 | Method for synthesizing biaromatic compound by coupling covalent organic framework material with photocatalysis C-C bond |
CN110818532A (en) * | 2019-10-18 | 2020-02-21 | 温州大学 | Method for preparing phenol and derivatives thereof by photocatalysis of metal-free halogenated aromatic hydrocarbon |
CN112724002A (en) * | 2020-12-31 | 2021-04-30 | 江汉大学 | Method for selectively reducing bromoacetophenone by alkali regulation and control and application |
CN114105746A (en) * | 2021-11-24 | 2022-03-01 | 温州大学 | Reduction dehalogenation method of photocatalysis alpha-halogenated carbonyl compound |
CN116102605A (en) * | 2023-01-18 | 2023-05-12 | 奥锐特药业股份有限公司 | Dehalogenation method of 9-halogenated steroid compound |
CN116102605B (en) * | 2023-01-18 | 2024-01-30 | 奥锐特药业股份有限公司 | Dehalogenation method of 9-halogenated steroid compound |
Also Published As
Publication number | Publication date |
---|---|
CN108002991B (en) | 2021-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108002991A (en) | A kind of visible light catalytic halogenated aryl hydrocarbon dehalogenation method without photoredox catalyst | |
Xie et al. | Visible-light-induced deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acids | |
Yang et al. | Highly efficient and selective photocatalytic hydrogenation of functionalized nitrobenzenes | |
Riente et al. | Application of metal oxide semiconductors in light-driven organic transformations | |
Srivastava et al. | Retracted Article: Eosin Y catalysed photoredox synthesis: a review | |
Li et al. | Visible light initiated hydrothiolation of alkenes and alkynes over ZnIn 2 S 4 | |
Peiris et al. | Metal nanoparticle photocatalysts: emerging processes for green organic synthesis | |
Zhang et al. | Visible light induced cyclopropanation of dibromomalonates with alkenes via double-SET by photoredox catalysis | |
Liu et al. | Organic dye photocatalyzed α-oxyamination through irradiation with visible light | |
Xiong et al. | Manganese (III)‐Mediated and‐Catalyzed Decarboxylative Hydroxysulfonylation of Arylpropiolic Acids with Sodium Sulfinates in Water | |
Li et al. | Cercosporin-bioinspired selective photooxidation reactions under mild conditions | |
Zhu et al. | Nickel-catalyzed sonogashira C (sp)–C (sp2) coupling through visible-light sensitization | |
Song et al. | External photocatalyst-free CH alkylation of N-sulfonyl ketimines with alkanes under visible light | |
Lu et al. | [3+ 2] Photooxygenation of aryl cyclopropanes via visible light photocatalysis | |
Yadav et al. | Visible-light-mediated efficient conversion of aldoximes and primary amides into nitriles | |
CN109438156A (en) | Method for dehalogenation conversion of halogenated hydrocarbon by photocatalysis | |
Park et al. | Synthesis of β‐Trifluoromethylated Ketones from Propargylic Alcohols by Visible Light Photoredox Catalysis | |
Borra et al. | Photocatalyst‐Free Visible‐Light Enabled Synthesis of Substituted Pyrroles from α‐Keto Vinyl Azides | |
Wang et al. | Visible-light-induced 1, 2-alkylarylation of alkenes with aC (sp3)–H bonds of acetonitriles involving neophyl rearrangement under transition-metal-free conditions | |
CN110386885A (en) | A kind of visible light promotion β-carbonyl sulphones preparation method | |
Li et al. | Metal-free photocatalyzed cross coupling of aryl (heteroaryl) bromides with isonitriles | |
Redon et al. | Metal-Free ipso-Selenocyanation of Arylboronic Acids Using Malononitrile and Selenium Dioxide | |
Chen et al. | The coupling of alkylboronic acids with α-(trifluoromethyl) styrenes by Lewis base/photoredox dual catalysis | |
Buxaderas et al. | Synthesis of Dihydroisobenzofurans via Palladium‐Catalyzed Sequential Alkynylation/Annulation of 2‐Bromobenzyl and 2‐Chlorobenzyl Alcohols under Microwave Irradiation | |
Li et al. | Visible-light-initiated catalyst-free oxidative cleavage of (Z)-triaryl-substituted alkenes containing pyridyl motif under ambient conditions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |