CN103833729B - Method for preparing coupling product and releasing hydrogen by visible light catalysis cross coupling - Google Patents

Method for preparing coupling product and releasing hydrogen by visible light catalysis cross coupling Download PDF

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CN103833729B
CN103833729B CN201210477433.7A CN201210477433A CN103833729B CN 103833729 B CN103833729 B CN 103833729B CN 201210477433 A CN201210477433 A CN 201210477433A CN 103833729 B CN103833729 B CN 103833729B
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hydrogen
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visible light
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CN103833729A (en
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吴骊珠
钟建基
孟庆元
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Technical Institute of Physics and Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/62—Isoquinoline or hydrogenated isoquinoline ring systems

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Abstract

The invention discloses a method for preparing a coupling product and releasing hydrogen by visible light catalysis cross coupling. Adding tertiary amine, a nucleophilic reagent, cobalt complex 1 or cobalt complex 2 and eosin Y into a solvent to obtain a mixed solution, irradiating the mixed solution with visible light under the protection of inert gas to obtain a cross-coupling product of the tertiary amine and the nucleophilic reagent, and releasing hydrogen. The reaction can be realized by irradiating with visible light under the condition of inert gas, the reaction condition is mild, and the whole system has no additional electron donor or electron acceptor, thereby saving energy and protecting environment.

Description

A kind of visible light catalytic cross-coupling is prepared coupled product and is put the method for hydrogen
Technical field
The invention belongs to catalytic synthetic techniques field, relate to a kind of method that cross-coupling puts hydrogen, particularly the cross-coupling of a kind of visible light catalytic tertiary amine and nucleophilic reagent puts hydrogen methods.
Background technology
In chemical field, the reaction of high, the mild condition of development selectivity, environmental protection is the target that chemists pursue always.In traditional chemistry, often need to compare exacting terms, as high temperature, high pressure, strong acid, highly basic etc.Before a century, famous photochemical scholar Ciamician is with regard to bewrite and looked forward to light as a kind of clean energy in the advantage of ordering about in chemical reaction and importance.Since two thousand eight, visible light catalytic organic reaction achieves a series of achievement in research attracted people's attention.As, the Yoon group of Univ. of Wisconsin-Madison utilizes ruthenium complexe to achieve in a series of electron deficiency or electron rich olefin hydrocarbon molecules under visible light conditions or intermolecular cycloaddition reaction as photosensitizers; Stephenson group of Boston University utilizes the title complex of ruthenium or iridium to achieve the dehalogenation reaction of organic halogen, radical cycloaddition reaction and the linked reaction etc. of tertiary amine and nucleophilic reagent as photocatalyst, and has successfully been applied in by visible light catalytic in the committed step of complete synthesis reaction; Macmillan group of Princeton University adopts the visible light catalytic of ruthenium complexe and the combination of organocatalysis to achieve the Unsymmetrical alkylation of aldehyde α position, is also achieved the trifluoromethylation reaction of aromatic base in addition by visible light catalytic; The organic dye of Metalfree is also used in the cross-coupling reaction of visible light catalytic by groups such as Konig, WuLizhu.
At present, the system of visible light catalytic is by oxidant removal a part hydrogen, thus realizes two intermolecular cross-couplings.As Konig group and WuLizhu group report respectively using dyestuff eosin eosinY(sodium salt or tetra-n-butyl amine salt) as photosensitizers, in oxygen atmosphere, under the irradiation of visible ray, what achieve N-phenyltetrahydroisoq,inolines derivative and the nucleophilic reagents such as Xiao base Wan Ting ﹑ dialkyl malonate compounds intersects dehydrogenation coupling (Org.Lett.2011,13,3852, Chem.Eur.J.2012,18,620); C.R.J.Stephenson etc. are using bromo chloroform as terminal oxygenant, the title complex of many pyridines ruthenium is as photosensitizers, what achieve N-phenyltetrahydroisoq,inolines derivative and Xiao base Wan Ting ﹑ Yin Duo ﹑ alkynes analog derivative intersects dehydrogenation coupling (Org.Lett.2012,14,94).The optimal mode of cross-coupling reaction realizing " Atom economy (atomeconomy) " releases a part hydrogen successfully building carbon-carbon bond while, but in most cases owing to reacting the motivating force of releasing hydrogen gas not, be usually difficult to realize.So current most report is all take off by oxygenant the product that a part hydrogen obtains coupling, also without any patent and bibliographical information in the atmosphere of rare gas element, utilize visible light catalytic while realizing tertiary amine and nucleophilic reagent cross-coupling reaction, be attended by the releasing of hydrogen.
Summary of the invention
The object of the invention is to design a kind of visible light catalytic cross-coupling prepare coupled product and put the method for hydrogen, releasing hydrogen gas while it can realize the cross-coupling reaction of tertiary amine and nucleophilic reagent under visible light conditions, protection of inert gas.This reaction, using eosin W or W S as photosensitizers, using cobalt complex as catalyzer, namely can realize the cross-coupling of tertiary amine and nucleophilic reagent efficiently under protection of inert gas with radiation of visible light, and releasing hydrogen gas.
The invention provides a kind of visible light catalytic cross-coupling prepare coupled product and put the method for hydrogen, comprise the following steps: tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2, eosin W or W S are added in solvent, obtain mixing solutions, under protection of inert gas, use radiation of visible light mixing solutions, obtain the cross-coupling products of tertiary amine and nucleophilic reagent and releasing hydrogen gas;
Wherein, described nucleophilic reagent is dialkyl malonate, dialkyl phosphite or indole derivatives;
Described solvent is the mixed solvent of water or water and acetonitrile;
The structural formula of described cobalt complex 1 and cobalt complex 2 is as follows respectively:
Further, the structural formula of described tertiary amine is as follows:
In formula, X is H, Y is OCH 3; Y is H, X is H, F, Cl, Br, CH 3, OCH 3or CN.
The structural formula of described indole derivatives is:
In formula, R 1﹑ R 2﹑ R 3﹑ R 4﹑ R 5complete is H; Or, R 1﹑ R 2﹑ R 3﹑ R 4﹑ R 5in one be CH 3, all the other are H; Or, R 3﹑ R 4in one be OCH 3, all the other are H; Or, R 3﹑ R 4in one be COOCH 3, all the other are H; Or, R 3for NO 2, all the other are H; Or, R 4for Cl, all the other are H.
Described dialkyl malonate is dimethyl malonate, diethyl malonate or propanedioic acid dibenzyl ester.Described dialkyl phosphite is dimethylphosphite, diethyl phosphite or dibenzyl phosphite.
In actually operating, first tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2 or eosin W or W S can be dissolved in solvent respectively, obtain each solution, more each solution is mixed afterwards, obtain mixing solutions.Or tertiary amine and nucleophilic reagent are dissolved in same solvent, and cobalt complex 1 or cobalt complex 2 and eosin W or W S are dissolved in respective solvent respectively, afterwards again by these three solution mixing, obtain mixing solutions.Each solvent may be the same or different, but at least containing water.Such as, be dissolved in acetonitrile by tertiary amine and nucleophilic reagent, cobalt complex 1 is dissolved in water and acetonitrile mixing solutions, and eosin W or W S is dissolved in water.When solvent is the mixed solvent of water and acetonitrile, both blending ratios do not limit.The difference of ethane nitrile content can cause the difference of productive rate.
Preferably, when solvent is the mixed solvent of water and acetonitrile, the volume ratio of water and acetonitrile is not less than 1:9.
Further, described cobalt complex 1 is not less than 0.072mg:1mL with the ratio of solvent; Described cobalt complex 2 is not less than 0.084mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is not less than 0.136mg:1mL; The ratio of described tertiary amine and solvent is not less than 0.02mmol:1mL; The ratio of described indole derivatives and solvent is not less than 0.022mmol:1mL; The ratio of described dialkyl malonate and solvent is not less than 0.02mmol:1mL; The ratio of described dialkyl phosphite and solvent is not less than 0.02mmol:1mL.When reacting, only need meet minimum scope, concentration is excessive does not have many contributions to productive rate again, also can cause the waste of raw material.
Preferably, described cobalt complex 1 is 0.072 ~ 1.44mg:1mL with the ratio of solvent; Described cobalt complex 2 is 0.084 ~ 1.68mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is 0.136 ~ 0.72mg:1mL; The ratio of described tertiary amine and solvent is 0.02mmol:1mL; The ratio of described indole derivatives and solvent is 0.022 ~ 0.06mmol:1mL; The ratio of described dialkyl malonate and solvent is 0.02 ~ 0.06mmol:1mL; The ratio of described dialkyl phosphite and solvent is 0.02mmol:1mL.
Eosin W or W S is photosensitizers, and its structural formula is as follows:
Further, described radiation of visible light adopts the GreenLEDs of 525nm ± 10nm to irradiate, and illumination temperature is room temperature ~ 40 DEG C, and light application time is 12 ~ 16h.
The present invention has following beneficial effect:
1. this reaction just can realize with radiation of visible light under inert gas conditions, and reaction conditions is gentle.
2. what the catalyst system of reaction was used is all molecular catalyst, is conducive to the study mechanism carrying out such reaction further.
3. this catalyst system is relatively inexpensive photosensitizers and catalyzer, whole system economical environment-protective.
4. this catalyst system can realize the cross-coupling of tertiary amine and nucleophilic reagent under visible light illumination efficiently, and simultaneously releasing hydrogen gas, tertiary amine and nucleophilic reagent applied widely, whole system does not have additional electron donor or electron acceptor(EA), embody Atom economy, whole system environmental protection.
Embodiment
With specific embodiment, the present invention is described in detail below, but be not to concrete restriction of the present invention.
In the present invention, the preparation of cobalt complex 1 and cobalt complex 2 can with reference to the method (Inorg.Chem.1992,31,1152) of L.G.Marzilli group report.
Embodiment 1
With cobalt complex 1 for catalyzer, in 2mL water, add this catalyzer of 0.36mg; With eosin eosinY for photosensitizers, in 2mL water, add this photosensitizers of 0.7mg; By catalyst solution and photosensitizing agent solution mixing, obtain 4mL mixed aqueous solution.Get 0.1mmol tertiary amine-1(X, Y is H) ﹑ and 0.2mmol indoles-1(R 1﹑ R 2﹑ R 3﹑ R 4﹑ R 5for H) be dissolved in 1mL acetonitrile, obtain acetonitrile solution.Again 4mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 2.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -4m.Logical nitrogen deoxygenation 30min, with mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then the GreenLEDs of 525nm ± 10nm illumination 12h at 40 DEG C is used, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., the beautiful 7890II type in sky) detect the growing amount of hydrogen, probably there is the hydrogen of 227 μ L to produce.After reaction terminates, add extraction into ethyl acetate, use saturated common salt water washing, anhydrous sodium sulfate drying, be finally separated after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 6%, and the amounts of hydrogen of releasing is 10% relative to theoretical value.
Embodiment 2
With embodiment 1, difference is: add 1.44mg photosensitizers, and the concentration of photosensitizers is 4.0 × 10 -4m.The hydrogen of 315 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 11%, and the amounts of hydrogen of releasing is 14% relative to theoretical value.
Embodiment 3
With embodiment 1, difference is: add 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m.The hydrogen of 427 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 21%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of releasing is 19% relative to theoretical value.
Embodiment 4
With embodiment 1, difference is: add 3.44mg photosensitizers, and the concentration of photosensitizers is 1.0 × 10 -3m.The hydrogen of 435 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 22%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of releasing is 19% relative to theoretical value.
Embodiment 5
With embodiment 1, difference is: add 1.08mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 6.0 × 10 -4m.The hydrogen of 458 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 25%, and the productive rate of coupled product is 18%, and the amounts of hydrogen of releasing is 20% relative to theoretical value.
Embodiment 6
With embodiment 1, difference is: add 1.8mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 1.0 × 10 -3m.The hydrogen of 824 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 41%, and the productive rate of coupled product is 35%, and the amounts of hydrogen of releasing is 37% relative to theoretical value.
Embodiment 7
With embodiment 1, difference is: add 2.9mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 1.6 × 10 -3m.The hydrogen of 1.14mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 55%, and the productive rate of coupled product is 48%, and the amounts of hydrogen of releasing is 51% relative to theoretical value.
Embodiment 8
With embodiment 1, difference is: add 3.6mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.The hydrogen of 1.54mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 70%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of releasing is 69% relative to theoretical value.
Embodiment 9
With embodiment 1, difference is: add 7.2mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 4.0 × 10 -3m.The hydrogen of 1.60mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 75%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of releasing is 71% relative to theoretical value.
Embodiment 10
With embodiment 1, difference is: add 3.6mg catalyzer, 2.04mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m, illumination 16h at 40 DEG C.The hydrogen of 1.99mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 81%, and the amounts of hydrogen of releasing is 89% relative to theoretical value.
Embodiment 11
With embodiment 1, difference is: in 2.5mL water, add 3.6mg catalyzer; 2.04mg photosensitizers is added in 2.5mL water; Catalyst solution and photosensitizing agent solution mixing, obtain 5mL mixed aqueous solution.Tertiary amine-1 and indoles-1 are added, obtains 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Illumination 16h at 40 DEG C.The hydrogen of 358.4 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 20%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of releasing is 16% relative to theoretical value.
Embodiment 12
With embodiment 1, difference is: in 2.5mL water, add 3.6mg catalyzer; 2.04mg photosensitizers is added in 2.0mL water; Catalyst solution and photosensitizing agent solution mixing, obtain 4.5mL mixed aqueous solution.Get tertiary amine-1 and indoles-1 is dissolved in 0.5mL acetonitrile, then 4.5mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Illumination 16h at 40 DEG C.The hydrogen of 1.79mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 91%, and the productive rate of coupled product is 75%, and the amounts of hydrogen of releasing is 80% relative to theoretical value.
Embodiment 13
With embodiment 1, difference is: in 1.5mL water, add 3.6mg catalyzer; 2.04mg photosensitizers is added in 1.5mL water; Catalyst solution and photosensitizing agent solution mixing, obtain 3.0mL mixed aqueous solution.Get tertiary amine-1 and indoles-1 is dissolved in 2.0mL acetonitrile, then 3.0mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.The hydrogen of 1.39mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 68%, and the productive rate of coupled product is 55%, and the amounts of hydrogen of releasing is 62% relative to theoretical value.
Embodiment 14
With embodiment 1, difference is: in 2.0mL water, add 3.6mg catalyzer; 2.04mg photosensitizers is added in 2.0mL water; Catalyst solution and photosensitizing agent solution mixing, obtain 4.0mL mixed aqueous solution.Get tertiary amine-1 and 0.11mmol indoles-1 is dissolved in 1.0mL acetonitrile, then 4.0mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.The hydrogen of 1.29mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 61%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of releasing is 58% relative to theoretical value.
Embodiment 15
With embodiment 1, difference is: in 2.0mL water, add 3.6mg catalyzer; 2.04mg photosensitizers is added in 2.0mL water; Catalyst solution and photosensitizing agent solution mixing, obtain 4.0mL mixed aqueous solution.Get tertiary amine-1 and 0.3mmol indoles-1 is dissolved in 1.0mL acetonitrile, then 4.0mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.The hydrogen of 2.03mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 82%, and the amounts of hydrogen of releasing is 91% relative to theoretical value.
Embodiment 16
With cobalt complex 2 for catalyzer, add this catalyzer of 0.42mg in 2.0mL acetonitrile, obtain catalyzer acetonitrile solution; Get 0.1mmol tertiary amine-1 ﹑ and 0.2mmol indoles-1 to be dissolved in 1.0mL acetonitrile, obtain substrate solution; The catalyzer acetonitrile solution of 2mL is joined in substrate solution, obtains 3.0mL acetonitrile solution; With eosin eosinY for photosensitizers, in 2.0mL water, add this photosensitizers of 0.68mg; Again this 2.0mL aqueous solution is joined in 3.0mL acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 2.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -4m.Logical nitrogen deoxygenation 30min, with mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then the GreenLEDs of 525nm ± 10nm illumination 12h at 40 DEG C is used, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., the beautiful 7890II type in sky) detect the growing amount of hydrogen, probably there is the hydrogen of 113 μ L to produce.After reaction terminates, add extraction into ethyl acetate, use saturated common salt water washing, anhydrous sodium sulfate drying, be finally separated after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 10%, and the productive rate of coupled product is 3%, and the amounts of hydrogen of releasing is 5% relative to theoretical value.
Embodiment 17
With embodiment 16, difference is: add 1.4mg photosensitizers, and the concentration of photosensitizers is 4.0 × 10 -4m.The hydrogen of 213 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 12%, and the productive rate of coupled product is 6%, and the amounts of hydrogen of releasing is 9% relative to theoretical value.
Embodiment 18
With embodiment 16, difference is: add 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m.The hydrogen of 323 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 17%, and the productive rate of coupled product is 8%, and the amounts of hydrogen of releasing is 15% relative to theoretical value.
Embodiment 19
With embodiment 16, difference is: add 3.6mg photosensitizers, and the concentration of photosensitizers is 1.0 × 10 -3m.The hydrogen of 313 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 7%, and the amounts of hydrogen of releasing is 14% relative to theoretical value.
Embodiment 20
With embodiment 16, difference is: add 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m.The hydrogen of 463 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 24%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of releasing is 21% relative to theoretical value.
Embodiment 21
With embodiment 16, difference is: add 2.1mg catalyzer, 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 1.0 × 10 -3m.The hydrogen of 556 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 25%, and the productive rate of coupled product is 15%, and the amounts of hydrogen of releasing is 25% relative to theoretical value.
Embodiment 22
With embodiment 16, difference is: add 3.3mg catalyzer, 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 1.6 × 10 -3m.The hydrogen of 756 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 35%, and the productive rate of coupled product is 17%, and the amounts of hydrogen of releasing is 34% relative to theoretical value.
Embodiment 23
With embodiment 16, difference is: add 4.2mg catalyzer, 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.The hydrogen of 934 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 20%, and the amounts of hydrogen of releasing is 42% relative to theoretical value.
Embodiment 24
With embodiment 16, difference is: add 8.4mg catalyzer, 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 4.0 × 10 -3m.Probably having the hydrogen of 984 μ L to produce product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 21%, and the amounts of hydrogen of releasing is 44% relative to theoretical value.
Embodiment 25
With embodiment 16, difference is: add 4.2mg catalyzer, 2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Illumination 16h at 40 DEG C.The hydrogen of 1.32mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 65%, and the productive rate of coupled product is 25%, and the amounts of hydrogen of releasing is 59% relative to theoretical value.
Embodiment 26
With embodiment 16, difference is: add 4.2mg catalyzer, 0.11mmol indoles-1,2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Illumination 16h at 40 DEG C.The hydrogen of 960 μ L is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 15%, and the amounts of hydrogen of releasing is 43% relative to theoretical value.
Embodiment 27
With embodiment 16, difference is: add 4.2mg catalyzer, 0.3mmol indoles-1,2.1mg photosensitizers, and the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Illumination 16h at 40 DEG C.The hydrogen of 1.37mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 65%, and the productive rate of coupled product is 26%, and the amounts of hydrogen of releasing is 61% relative to theoretical value.
Embodiment 28
With cobalt complex 1 for catalyzer, in 2mL water, add this catalyzer of 3.6mg; With eosin eosinY for photosensitizers, in 2mL water, add this photosensitizers of 2.04mg; By catalyst solution and photosensitizing agent solution mixing, obtain 4mL mixed aqueous solution; Getting 0.1mmol tertiary amine-2(X is CH 3, Y is that H) ﹑ and 0.2mmol indoles-1 are dissolved in 1mL acetonitrile, then 4mL mixed aqueous solution is joined this acetonitrile solution, obtains 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Logical nitrogen deoxygenation 30min, with mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then the GreenLEDs of 525nm ± 10nm illumination 16h at 40 DEG C is used, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., the beautiful 7890II type in sky) detect the growing amount of hydrogen, probably there is the hydrogen of 2.23mL to produce.After reaction terminates, add extraction into ethyl acetate, use saturated common salt water washing, anhydrous sodium sulfate drying, be finally separated after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-p-methylphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 95%, and the amounts of hydrogen of releasing is 100% relative to theoretical value.
Embodiment 29
With embodiment 28, difference is: adding tertiary amine-3(X is OCH 3, Y is H) and replace tertiary amine-2(X to be CH 3, Y is H).The hydrogen of 1.61mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-p-methoxyphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 80%, and the productive rate of coupled product is 65%, and the amounts of hydrogen of releasing is 72% relative to theoretical value.
Embodiment 30
With embodiment 28, difference is: to add tertiary amine-4(X be H, Y is OCH 3) replace tertiary amine-2(X to be CH 3, Y is H).The hydrogen of 1.37mL is probably had to produce.Product is 1-(1H-indol-3-yl)-2-o-methoxyphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 70%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of releasing is 61% relative to theoretical value.
Embodiment 31
With embodiment 28, difference is: to add tertiary amine-5(X be F, Y is H) replace tertiary amine-2(X to be CH 3, Y is H).The hydrogen of 2.22mL is probably had to produce.Product be 1-(1H-indol-3-yl)-2-to fluorophenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 94%, and the amounts of hydrogen of releasing is 99% relative to theoretical value.
Embodiment 32
With embodiment 28, difference is: to add tertiary amine-6(X be Br, Y is H) replace tertiary amine-2(X to be CH 3, Y is H).The hydrogen of 918 μ L is probably had to produce.Product be 1-(1H-indol-3-yl)-2-to bromophenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 41%, and the amounts of hydrogen of releasing is 41% relative to theoretical value.
Embodiment 33
With embodiment 28, difference is: to add tertiary amine-7(X be CN, Y is H) replace tertiary amine-2(X to be CH 3, Y is H).The hydrogen of 650 μ L is probably had to produce.Product be 1-(1H-indol-3-yl)-2-to cyano-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 40%, and the productive rate of coupled product is 32%, and the amounts of hydrogen of releasing is 29% relative to theoretical value.
Embodiment 34
With cobalt complex 1 for catalyzer, in 2mL water, add this catalyzer of 3.6mg; With eosin eosinY for photosensitizers, in 2mL water, add this photosensitizers of 2.04mg; By catalyst solution and photosensitizing agent solution mixing, obtain 4mL mixed aqueous solution; Get 0.1mmol tertiary amine-1 ﹑ and 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H) be dissolved in 1mL acetonitrile, then 4mL mixed aqueous solution is joined this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10 -4m, the concentration of catalyzer is 2.0 × 10 -3m.Logical nitrogen deoxygenation 30min, with mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then the GreenLEDs of 525nm ± 10nm illumination 16h at 40 DEG C is used, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., the beautiful 7890II type in sky) detect the growing amount of hydrogen, probably there is the hydrogen of 1.8mL to produce.After reaction terminates, add extraction into ethyl acetate, use saturated common salt water washing, anhydrous sodium sulfate drying, be finally separated after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(N-skatole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 72%, and the amounts of hydrogen of releasing is 81% relative to theoretical value.
Embodiment 35
With embodiment 34, difference is: add indoles-3(R 2for CH 3, R 1﹑ R 3﹑ R 4﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 2.23mL is probably had to produce.Product is 1-(2 methyl indole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 98%, and the amounts of hydrogen of releasing is 100% relative to theoretical value.
Embodiment 36
With embodiment 34, difference is: add indoles-4(R 4for CH 3, R 1﹑ R 2﹑ R 3﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 2.15mL is probably had to produce.Product is 1-(6-skatole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 90%, and the amounts of hydrogen of releasing is 96% relative to theoretical value.
Embodiment 37
With embodiment 34, difference is: add indoles-5(R 4for OCH 3, R 1﹑ R 2﹑ R 3﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.86mL is probably had to produce.Product is 1-(6-methoxy-Indole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 78%, and the amounts of hydrogen of releasing is 82% relative to theoretical value.
Embodiment 38
With embodiment 34, difference is: add indoles-6(R 4for Cl, R 1﹑ R 2﹑ R 3﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.19mL is probably had to produce.Product is 1-(6-chloro-indole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 60%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of releasing is 53% relative to theoretical value.
Embodiment 39
With embodiment 34, difference is: add indoles-7(R 4for COOCH 3, R 1﹑ R 2﹑ R 3﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.7mL is probably had to produce.Product is 1-(6-methyl-formiate base indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 67%, and the amounts of hydrogen of releasing is 76% relative to theoretical value.
Embodiment 40
With embodiment 34, difference is: add indoles-8(R 3for CH 3, R 1﹑ R 2﹑ R 4﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 2.15mL is probably had to produce.Product is 1-(5-skatole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 84%, and the amounts of hydrogen of releasing is 96% relative to theoretical value.
Embodiment 41
With embodiment 34, difference is: add indoles-9(R 3for OCH 3, R 1﹑ R 2﹑ R 4﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.95mL is probably had to produce.Product is 1-(5-methoxy-Indole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 71%, and the amounts of hydrogen of releasing is 87% relative to theoretical value.
Embodiment 42
With embodiment 34, difference is: add indoles-10(R 3for COOCH 3, R 1﹑ R 2﹑ R 4﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.3mL is probably had to produce.Product is 1-(5-methyl-formiate base indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 60%, and the productive rate of coupled product is 54%, and the amounts of hydrogen of releasing is 58% relative to theoretical value.
Embodiment 43
With embodiment 34, difference is: add indoles-11(R 3for NO 2, R 1﹑ R 2﹑ R 4﹑ R 5for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 224 μ L is probably had to produce.Product is 1-(5-nitroindoline-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 5%, and the amounts of hydrogen of releasing is 10% relative to theoretical value.
Embodiment 44
With embodiment 34, difference is: add indoles-12(R 5for CH 3, R 1﹑ R 2﹑ R 3﹑ R 4for H) replace indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.97mL is probably had to produce.Product is 1-(7-skatole-3-base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 95%, and the productive rate of coupled product is 83%, and the amounts of hydrogen of releasing is 88% relative to theoretical value.
Embodiment 45
With embodiment 34, difference is: add 0.3mmol dimethyl malonate and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.07mL is probably had to produce.Product is 1-(2-malonic acid dimethyl ester group)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 85%, and the productive rate of coupled product is 33%, and the amounts of hydrogen of releasing is 48% relative to theoretical value.
Embodiment 46
With embodiment 34, difference is: add 0.1mmol dimethyl malonate and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 780 μ L is probably had to produce.Product is 1-(2-malonic acid dimethyl ester group)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 80%, and the productive rate of coupled product is 23%, and the amounts of hydrogen of releasing is 35% relative to theoretical value.
Embodiment 47
With embodiment 34, difference is: add 0.1mmol propanedioic acid dibenzyl ester and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.0mL is probably had to produce.Product is 1-(2-propanedioic acid dibenzyl ester group)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 43%, and the amounts of hydrogen of releasing is 45% relative to theoretical value.
Embodiment 48
With embodiment 34, difference is: add 0.1mmol diethyl malonate and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.34mL is probably had to produce.Product is 1-(2-diethyl malonate base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 43%, and the amounts of hydrogen of releasing is 60% relative to theoretical value.
Embodiment 49
With embodiment 34, difference is: add 0.1mmol dimethylphosphite and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.79mL is probably had to produce.Product is 1-dimethyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 91%, and the productive rate of coupled product is 73%, and the amounts of hydrogen of releasing is 80% relative to theoretical value.
Embodiment 50
With embodiment 34, difference is: add 0.1mmol diethyl phosphite and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.79mL is probably had to produce.Product is 1-diethyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of releasing is 76% relative to theoretical value.
Embodiment 51
With embodiment 34, difference is: add 0.1mmol dibenzyl phosphite and replace 0.2mmol indoles-2(R 1for CH 3, R 2﹑ R 3﹑ R 4﹑ R 5for H).The hydrogen of 1.81mL is probably had to produce.Product is 1-dibenzyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 95%, and the productive rate of coupled product is 72%, and the amounts of hydrogen of releasing is 81% relative to theoretical value.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.

Claims (7)

1. a visible light catalytic cross-coupling is prepared coupled product and puts the method for hydrogen, it is characterized in that, comprise the following steps: tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2, eosin W or W S are added in solvent, obtain mixing solutions, under protection of inert gas, use radiation of visible light mixing solutions, obtain the cross-coupling products of tertiary amine and nucleophilic reagent and releasing hydrogen gas;
Wherein, described nucleophilic reagent is dialkyl malonate, dialkyl phosphite or indole derivatives;
Described solvent is the mixed solvent of water or water and acetonitrile;
The structural formula of described cobalt complex 1 and cobalt complex 2 is as follows respectively:
The structural formula of described tertiary amine is as follows:
In formula, X is H, Y is OCH 3; Y is H, X is H, F, Cl, Br, CH 3, OCH 3or CN.
2. visible light catalytic cross-coupling according to claim 1 is prepared coupled product and is put the method for hydrogen, it is characterized in that,
The structural formula of described indole derivatives is:
In formula, R 1﹑ R 2﹑ R 3﹑ R 4﹑ R 5complete is H; Or, R 1﹑ R 2﹑ R 3﹑ R 4﹑ R 5in one be CH 3, all the other are H; Or, R 3﹑ R 4in one be OCH 3, all the other are H; Or, R 3﹑ R 4in one be COOCH 3, all the other are H; Or, R 3for NO 2, all the other are H; Or, R 4for Cl, all the other are H.
3. visible light catalytic cross-coupling according to claim 1 is prepared coupled product and is put the method for hydrogen, it is characterized in that, described dialkyl malonate is dimethyl malonate, diethyl malonate or propanedioic acid dibenzyl ester.Described dialkyl phosphite is dimethylphosphite, diethyl phosphite or dibenzyl phosphite.
4. visible light catalytic cross-coupling according to claim 1 is prepared coupled product and is put the method for hydrogen, it is characterized in that, when solvent is the mixed solvent of water and acetonitrile, the volume ratio of water and acetonitrile is not less than 1:9.
5. visible light catalytic cross-coupling according to claim 1 is prepared coupled product and is put the method for hydrogen, it is characterized in that, described cobalt complex 1 is not less than 0.072mg:1mL with the ratio of solvent; Described cobalt complex 2 is not less than 0.084mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is not less than 0.136mg:1mL; The ratio of described tertiary amine and solvent is not less than 0.02mmol:1mL; The ratio of described indole derivatives and solvent is not less than 0.022mmol:1mL; The ratio of described dialkyl malonate and solvent is not less than 0.02mmol:1mL; The ratio of described dialkyl phosphite and solvent is not less than 0.02mmol:1mL.
6. visible light catalytic cross-coupling is prepared coupled product and is put the method for hydrogen according to claim 1 or 5, it is characterized in that, described cobalt complex 1 is 0.072 ~ 1.44mg:1mL with the ratio of solvent; Described cobalt complex 2 is 0.084 ~ 1.68mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is 0.136 ~ 0.72mg:1mL; The ratio of described tertiary amine and solvent is 0.02mmol:1mL; The ratio of described indole derivatives and solvent is 0.022 ~ 0.06mmol:1mL; The ratio of described dialkyl malonate and solvent is 0.02 ~ 0.06mmol:1mL; The ratio of described dialkyl phosphite and solvent is 0.02mmol:1mL.
7. visible light catalytic cross-coupling according to claim 1 is prepared coupled product and is put the method for hydrogen, it is characterized in that, described radiation of visible light adopts the GreenLEDs of 525nm ± 10nm to irradiate, and illumination temperature is room temperature ~ 40 DEG C, and light application time is 12 ~ 16h.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497585A (en) * 2008-01-31 2009-08-05 中国科学院理化技术研究所 Method for photocatalytic synthesis of 1,3, 5-trisubstituted-2-pyrazole derivatives

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497585A (en) * 2008-01-31 2009-08-05 中国科学院理化技术研究所 Method for photocatalytic synthesis of 1,3, 5-trisubstituted-2-pyrazole derivatives

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Eosin Y Catalyzed Visible Light Oxidative C–C and C–P bond Formation;Durga Prasad Hari et al;《Org. Lett.》;20110711;第13卷(第15期);3852–3855 *
曙红_碳纳米管_CuO_CoO体系的光催化还原水制氢性能;穆劲 等;《无机化学学报》;20120228;第28卷(第2期);251-256 *

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