CN109317202A - A kind of polycarbazole load nano palladium material and the preparation method and application thereof - Google Patents

A kind of polycarbazole load nano palladium material and the preparation method and application thereof Download PDF

Info

Publication number
CN109317202A
CN109317202A CN201811314978.XA CN201811314978A CN109317202A CN 109317202 A CN109317202 A CN 109317202A CN 201811314978 A CN201811314978 A CN 201811314978A CN 109317202 A CN109317202 A CN 109317202A
Authority
CN
China
Prior art keywords
polycarbazole
reaction
nano
boric acid
palladium material
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
Application number
CN201811314978.XA
Other languages
Chinese (zh)
Other versions
CN109317202B (en
Inventor
李红喜
郭斌
郎建平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201811314978.XA priority Critical patent/CN109317202B/en
Publication of CN109317202A publication Critical patent/CN109317202A/en
Application granted granted Critical
Publication of CN109317202B publication Critical patent/CN109317202B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring

Abstract

The invention discloses a kind of polycarbazole load nano palladium materials and the preparation method and application thereof.Specifically, the average particle size distribution of Pd nano particle prepared by the present invention is dispersed on substrate polycarbazole material in 4.2 nm or so.The material can be catalyzed the Suzuki reaction that aryl bromide and aryl chloride participate under the conditions of illumination, water phase, have the characteristics that high conversion efficiency, applied widely, reaction condition is green mild.After conversion reaction, substrate is isolated from reaction system, catalyst system can carry out next round reaction, still be able to maintain stable and its catalytic activity after circulation 3 times and also not be substantially reduced.

Description

A kind of polycarbazole load nano palladium material and the preparation method and application thereof
Technical field
The invention belongs to technical field of catalytic chemistry, it is related to nanometer Pd material and its preparation of a kind of carbazole polymer load Method and application.
Background technique
Diaryl, polyarylate have been widely used for manufacture medicine, chemical agricultural product, natural products artificial substituting Product, dyestuff and fragrance.Currently, the main method for synthesizing this kind of compound has very much, at present for synthesizing this kind of compound Repercussion study mainly still concentrate on heating reaction using homogeneous catalyst and carry out, to overcome required for its catalytic cycle Driving force.There is many shortcomings for these catalyst systems, make as catalyst remains in the product, catalyst is not recyclable With, need high temperature or electronics sacrifice agent to promote to react, be easy to cause environmental pollution etc..
To overcome the above disadvantages, more and more researchs all concentrate on developing heterogeneous catalysis, although heterogeneous urge Agent overcomes some of which difficulty, but haves the defects that reaction temperature height and electronics sacrifice agent.To overcome the two to ask Topic combines solution other problems, and the heterogeneous catalysis of photoinduction enters the visual field of people.
In recent years, having seminar uses metal oxide as carrier loaded Pd nano particle or Polarium, still It is hardly seen that the polymer with visible absorption is used to realize that light promotes reaction as carrier loaded Pd nano particle, and Prior art substrate is concentrated mainly on aryl iodide and aryl bromide, and using aryl chloride as the visible light-inducing of substrate Reaction does not have been reported that.Aryl chloride is more stable than aryl iodide and aryl bromide, the fracture of C-Cl difficulty and activation, the work of C-Cl Change and generally requires high temperature and big steric hindrance, toxic Phosphine ligands participation.
Summary of the invention
For above situation, the purpose of the present invention is to provide a kind of nanometer Pd material of Polymer-supported and its preparation sides Method and purposes.Using the nanometer Pd material of the Polymer-supported as catalyst, in aqueous solvent, photocatalysis aromatic bromide or virtue The Suzuki reaction of fragrant chloride and fragrant boric acid, is finally made biaryl compound.In addition, making in above-mentioned reaction system The nanometer Pd material of the Polymer-supported used for catalyst can be recycled 3 times or more, still stable after circulation 3 times, And its catalytic activity is not also substantially reduced, is a kind of effective and efficient catalyst.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of polycarbazole load nano palladium material, Technique of Nano Pd are distributed on carbazole polymer；Its substrate is carbazole polymer, nanometer Palladium particle is evenly distributed in substrate with the average grain diameter of 4~4.5 nm preferably 4.2 nm, the chemical valence that wherein Metal Palladium is presented It is respectively pyridine type and pyrroles of type that for zeroth order, in polymer, nitrogen, which shows two kinds of existence forms,；Preferably, polycarbazole loads In nano palladium material, the load capacity of palladium is 1.3 wt of wt %~1.4 %.
A kind of preparation method of polycarbazole load nano palladium material, includes the following steps: under inert gas, will contain Pd (OAc)2NaBH is added after being stirred with the aqueous solution of polycarbazole4Aqueous solution, then continue to be stirred to react, obtain poly- click Azoles loads nano palladium material.
In above-mentioned technical proposal, centrifugal treating after being stirred to react, sediment is successively washed with water, ethyl alcohol, ether, so After be dried in vacuo, obtain polycarbazole load nano palladium material.
In above-mentioned technical proposal, the mixing speed being stirred is 1000 rpms, and the time is 0.5 hour；Stirring is anti- The mixing speed answered is 1000 rpms, and the time is 4 hours.
In above-mentioned technical proposal, polycarbazole is loaded in nano palladium material, and the load capacity of palladium is the 1.3 wt % of wt %~1.4, The mass percent that can use between Metal Palladium and polymer material obtains.
In above-mentioned technical proposal, any one of the inert gas in nitrogen, argon gas, preferably nitrogen.
The preparation method of above-mentioned polycarbazole load nano palladium material can be expressed as follows: under a nitrogen atmosphere, by Pd (OAc)2 It is stirred 0.5 hour on magnetic stirring apparatus with 1000 rpms of speed with the suspension of polycarbazole, afterwards with syringe to molten NaBH is added in liquid4Aqueous solution, then continue to be stirred to react 4 hours；Aqueous solvent is removed by centrifugation after reaction, obtains Sediment successively washed with water, ethyl alcohol, ether, be then dried in vacuo, obtain polycarbazole load nano palladium material (Pd/P3,5- DiCzPy).
Polycarbazole loads nano palladium material and prepares biaryl compound in photocatalysis aromatic halides and fragrant acid reaction In application；In the polycarbazole load nano palladium material, Technique of Nano Pd is distributed on carbazole polymer, and substrate is carbazole polymerization Object, palladium nanoparticles are evenly distributed in substrate with the average grain diameter of 4.2 nm, and the chemical valence that wherein Metal Palladium is presented is zeroth order, It is respectively pyridine type and pyrroles of type that nitrogen, which shows two kinds of existence forms, in polymer；Preferably, polycarbazole loads Technique of Nano Pd In material, the load capacity of palladium is 1.3 wt of wt %~1.4 %.
In above-mentioned technical proposal, aromatic halides are aromatic bromide or aromatic chlorides.The aromatic bromide is selected from Bromobenzene, alkyl substituted phenyl-bromide, alkoxy substituted phenyl-bromide, acetyl group substituted phenyl-bromide, formoxyl substituted phenyl-bromide, cyano substituted phenyl-bromide, Any one in nitro substituted phenyl-bromide, naphthalene bromine and hetero-aromatic ring bromide；The aromatic chlorides are selected from chlorobenzene, acetyl group replaces Chlorobenzene, formoxyl replace any one in chlorobenzene, cyano substitution chlorobenzene, nitro substitution chlorobenzene, naphthalene chlorine and hetero-aromatic ring chloride； The fragrance boronic acid compounds are selected from phenyl boric acid, alkyl substituted benzene boric acid, alkoxy substituted boric acid, acetyl group substituted benzene boron Acid, formoxyl replace phenyl boric acid, nitro to replace phenyl boric acid, cyano that phenyl boric acid, ester group is replaced to replace phenyl boric acid, naphthalene boronic acids and heterocycle Any one in boric acid.
In above-mentioned technical proposal, aromatic halides and fragrant acid reaction prepare biaryl compound in the presence of a base, It is carried out in the presence of water, in nitrogen or argon gas；Preferably, aromatic halides, fragrant boric acid, polycarbazole load Technique of Nano Pd material Expect, the amount ratio of alkali is 0.2 mol:0..3 mol:8 mg:0.3 mol.
In above-mentioned technical proposal, the alkali is selected from potassium phosphate.
In above-mentioned technical proposal, the solvent is water, any one in n,N-Dimethylformamide, preferably water.
In above-mentioned technical proposal, the temperature of the reaction is room temperature.
In above-mentioned technical proposal, the illumination condition is that blue LED lamp shines condition.
In above-mentioned technical proposal, when the time of the reaction is 12~48, it is preferred that when aromatic halides are aromatic bromination When object, the time of reaction is 12 hours；When aromatic halides are aromatic chlorides, the time of reaction is 48 hours.
Specifically, polycarbazole load nano palladium material photocatalysis aromatic halides and fragrant acid reaction prepare diaryl Compound includes the following steps:
According to aromatic halides: fragrant boric acid: polycarbazole loads nano palladium material: alkali=0.2 mol:0..3 mol:8 mg: The ratio of 0.3 mol, under a nitrogen atmosphere by aromatic halides, fragrant boric acid, polycarbazole load nano palladium material, alkali and solvent It is added in crystal reaction tube, the room temperature confined reaction under blue LED lamp irradiation condition；After reaction, it is filtered to remove poly- click Azoles loads nano palladium material, and water is added and ethyl acetate extracts filtrate, merges organic phase, dense through drying, filtering, decompression Contracting, silica gel chromatography, obtain biaryl compound.
A kind of method of synthesis of diaryl compound, includes the following steps:
Aromatic halides, fragrant boric acid, polycarbazole load nano palladium material, alkali and solvent are added to quartz under a nitrogen atmosphere In reaction tube, room temperature confined reaction, obtains biaryl compound under illumination condition；Preferably, after reaction, it is filtered to remove Polycarbazole loads nano palladium material, and water then is added and ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains biaryl compound.
In above-mentioned technical proposal, in the polycarbazole load nano palladium material, Technique of Nano Pd is distributed on carbazole polymer, Substrate is carbazole polymer, and palladium nanoparticles are evenly distributed in substrate with the average grain diameter of 4.2 nm, and wherein Metal Palladium is presented Chemical valence be zeroth order, it is respectively pyridine type and pyrroles of type that nitrogen, which shows two kinds of existence forms, in polymer；Preferably, gather Carbazole loads in nano palladium material, and the load capacity of palladium is 1.3 wt of wt %~1.4 %.
In above-mentioned technical proposal, aromatic halides are aromatic bromide or aromatic chlorides.The aromatic bromide is selected from Bromobenzene, alkyl substituted phenyl-bromide, alkoxy substituted phenyl-bromide, acetyl group substituted phenyl-bromide, formoxyl substituted phenyl-bromide, cyano substituted phenyl-bromide, Any one in nitro substituted phenyl-bromide, naphthalene bromine and hetero-aromatic ring bromide；The aromatic chlorides are selected from chlorobenzene, acetyl group replaces Chlorobenzene, formoxyl replace any one in chlorobenzene, cyano substitution chlorobenzene, nitro substitution chlorobenzene, naphthalene chlorine and hetero-aromatic ring chloride； The fragrance boronic acid compounds are selected from phenyl boric acid, alkyl substituted benzene boric acid, alkoxy substituted boric acid, acetyl group substituted benzene boron Acid, formoxyl replace phenyl boric acid, nitro to replace phenyl boric acid, cyano that phenyl boric acid, ester group is replaced to replace phenyl boric acid, naphthalene boronic acids and heterocycle Any one in boric acid.
In above-mentioned technical proposal, aromatic halides, fragrant boric acid, polycarbazole load nano palladium material, the amount ratio of alkali is 0.2 mol:0..3 mol:8 mg:0.3 mol。
In above-mentioned technical proposal, the alkali is selected from potassium phosphate.
In above-mentioned technical proposal, the solvent is water, any one in n,N-Dimethylformamide, preferably water.
In above-mentioned technical proposal, the temperature of the reaction is room temperature.
In above-mentioned technical proposal, the illumination condition is that blue LED lamp shines condition.
In above-mentioned technical proposal, when the time of the reaction is 12~48, it is preferred that when aromatic halides are aromatic bromination When object, the time of reaction is 12 hours；When aromatic halides are aromatic chlorides, the time of reaction is 48 hours.
Compared with prior art, the present invention by adopting the above technical scheme has the advantage that
(1) present invention discloses a kind of nanometer Pd material that the carbazole object as catalyst loads for the first time, can be in illumination item Catalysis prepares biaryl compound using aromatic bromide or aromatic chlorides and fragrant boric acid as the reaction of raw material under part；
(2) present invention in record carbazole polymer load nanometer Pd material have be evenly distributed, average particle size distribution 4.2 Nm, Pd nano particle chemical valence be the features such as 0 valence, nitrogen show two kinds of forms of pyridine type and pyrroles of type；
(3) reaction recorded in the present invention has the characteristics that high conversion efficiency, applied widely, reaction condition is green mild；
(4) after conversion reaction, the objects such as reaction are extracted from reaction system, new reaction substrate is added to reaction system In, next round reaction can be carried out, the nanometer Pd material of carbazole object load can be recycled at least 3 times, remain to protect after circulation 3 times It is fixed to keep steady, and its catalytic activity is not also substantially reduced；It ' for the reaction of-bromoacetophenone and phenyl boric acid, is recycled 3 times by 4 Yield be followed successively by 95%, 94% and 93%, and recycle catalysis after transmission electron microscope (TEM) and photoelectron spectroscopy (XPS) characterize table Bright metal nanoparticle is substantially unchanged.
Detailed description of the invention
Fig. 1 is the powder XRD pattern for the nanometer Pd material that carbazole polymer of the invention loads, powder X-ray RD diffraction maximum By the way that the characteristic peak of Metal Palladium can be attributed to compared with standard PDF card；
Fig. 2 is the photoelectron spectroscopy for the nanometer Pd material palladium that carbazole polymer of the invention loads, and illustrates being primarily present for palladium Form is zeroth order palladium, wherein the divalent palladium not restored completely with the presence of part；
Fig. 3 is the photoelectron spectroscopy for the nanometer Pd material nitrogen that carbazole polymer of the invention loads, nitrogen before and after comparison Metal Supported Photoelectron spectroscopy, in conjunction with can be reduced, caused by this is the coordination between nitrogen palladium；
Fig. 4 is the transmission electron microscope and grain size distribution for the nanometer Pd material that carbazole polymer of the invention loads, and can therefrom be seen Pd nano particle being uniformly distributed on carrier out, partial size compare concentration, and average grain diameter is 4.2 nanometers；
Fig. 5 is the high-resolution-ration transmission electric-lens figure for the nanometer Pd material that carbazole polymer of the invention loads, and can therefrom be observed (111) crystal face of Metal Palladium, interplanar distance are 0.228nm and theoretical value 0.225nm close；
Fig. 6 is that the distribution diagram of element for the nanometer Pd material that carbazole polymer of the invention loads illustrates the uniform of C, N, Pd element Distribution；
Fig. 7 is that the nanometer Pd material that carbazole polymer of the invention loads is utilized as 2 reaction cycle of catalyst embodiment Efficiency chart, there it can be seen that catalyst keeps higher efficiency during recycling, under obvious Drop；
Fig. 8 is that the nanometer Pd material that carbazole polymer of the invention loads recycles later transmission electron microscope and particle diameter distribution Figure, it can be seen that Pd nano particle is still uniformly distributed on carrier, partial size compares concentration, and average grain diameter is 5.1 nanometers；
Fig. 9 is that the nanometer Pd material that carbazole polymer of the invention loads recycles later powder XRD pattern, powder There is no variations for XRD diffraction maximum, by that can be attributed to the characteristic peak of Metal Palladium compared with standard PDF card；
Figure 10 is the photoelectron spectroscopy that the nanometer Pd material that carbazole polymer of the invention loads recycles later palladium, explanation The existence form of palladium is zeroth order palladium.
Specific embodiment
Further description is made to the present invention below in conjunction with the drawings and specific embodiments.Unless otherwise indicated, following Reagent used in embodiment, material, instrument etc. can be obtained by commercial means.
Embodiment 1
By Pd (OAc)2(11.2 mg), carbazole polymer (120 mg) are added to the circle of 100 ml, tri- neck containing magnetic stir bar In the flask of bottom, stirs at room temperature 30 minutes, NaBH is then added by syringe thereto4(0.05 M, 5.0 mL's) is water-soluble Liquid reacts 4 hours at room temperature；After reaction, it is centrifugated out solid, is successively washed with water, ethyl alcohol and ether, then vacuum It is dry to load nano palladium material (Pd/P3,5-diCzPy) to get corresponding polycarbazole.
Icp analysis shows that the load capacity of palladium is 1.37% wt.
Fig. 1 to Fig. 6 is successively powder XRD pattern, the photoelectricity of the nanometer Pd material of carbazole polymer load of the invention Sub- energy spectrum diagram, transmission electron microscope and particle diameter distribution, high-resolution-ration transmission electric-lens and distribution diagram of element；Powder X-ray RD diffraction maximum by with Standard PDF card compares, and can be attributed to the characteristic peak of Metal Palladium；The photoelectron spectroscopy of palladium further illustrates mainly depositing for palladium It is zeroth order palladium in form；The photoelectron spectroscopy of Metal Supported front and back nitrogen is compared, in conjunction with that can be reduced, this is between nitrogen palladium Caused by coordination；From can be seen that Pd nano particle being uniformly distributed on carrier in transmission electron microscope picture, high-resolution is saturating Radio mirror has then observed (111) crystal face of Metal Palladium, and interplanar distance is 0.228nm and theoretical value 0.225nm close, element Distribution map then further illustrates being uniformly distributed for C, N, Pd element.
Embodiment 2
4 '-bromoacetophenones (40 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- 4-acetylbiphenyl (yield 94%)；Using palladium-carbon catalyst, yield 12%, using chlorination Palladium yield is 29%.
The nuclear magnetic data of products therefrom is as follows:
1H NMR (600 MHz, CDCl3) δ 8.03 (t, J = 6.9 Hz, 2H), 7.68 (dd, J = 7.5, 6.3 Hz, 2H), 7.63 (dd, J = 10.2, 3.2 Hz, 2H), 7.52–7.44 (m, 2H), 7.43–7.37 (m, 1H), 2.64 (d, J = 5.5 Hz, 3H).
13C NMR (151 MHz, CDCl3) δ 197.9, 146.0, 140.1, 136.0, 129.1, 129.1, 128.4, 127.5, 127.4, 26.9.
High resolution mass spectrum data is as follows:
C14H13O [M + H]+Theoretical value 197.0961, test value 197.0961.
It is above-mentioned after reaction, ether extract by way of, product is isolated from reaction system, then be added thereto 4 '-bromoacetophenones (40 mg) and phenyl boric acid (37 mg) carry out next round conversion reaction；Catalyst is carried out as procedure described above Recycle, it is as shown in Figure 2 that 3 yields of circulation are followed successively by 95%, 94% and 93%(its result), and recycle saturating after catalysis Radio mirror (TEM), powder X-ray RD and photoelectron spectroscopy (XPS) show metal nanoparticle, and without significant change, (its result is as schemed 7 to shown in Figure 10).
Embodiment 3
4 '-bromoacetophenones (40 mg), 4- methylphenylboronic acid (41 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphoric acid Potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-methyl -4- 4-acetylbiphenyls (yield 98%), if made using diisopropylamine For alkali, yield 16%.
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.1 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 7.8 Hz, 2H), 7.21 (d, J = 4.3 Hz, 2H), 2.58 (s, 3H), 2.36 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.0, 145.9, 138.4, 137.1, 135.8, 129.9, 129.1, 127.3, 127.2, 26.9, 21.4.
High resolution mass spectrum data is as follows:
C15H15O [M + H]+Theoretical value 211.1117, test value 211.1120.
Embodiment 4
4 '-bromoacetophenones (40 mg), 3- methylphenylboronic acid (41 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphoric acid Potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 3 '-methyl -4- 4-acetylbiphenyls (yield 94%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.2 Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H), 7.41 (d, J = 7.9 Hz, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.20 (d, J = 7.3 Hz, 1H), 2.62 (s, 3H), 2.42 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.0, 146.1, 140.1, 138.8, 136.0, 129.2, 129.1, 128.2, 127.4, 124.6, 26.9, 21.7.
High resolution mass spectrum data is as follows:
C15H15O [M + H]+Theoretical value 211.1117, test value 211.1125.
Embodiment 5
4 '-bromoacetophenones (40 mg), 2- methylphenylboronic acid (41 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphoric acid Potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 2 '-methyl -4- 4-acetylbiphenyls (yield 92%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.1 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H), 7.25 (dd, J = 20.4, 9.9 Hz, 5H), 2.65 (s, 3H), 2.27 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.1, 147.2, 140.9, 135.8, 135.4, 130.7, 129.7, 129.7, 128.4, 128.1, 126.1, 26.9, 20.6.
High resolution mass spectrum data is as follows:
C15H15O [M + H]+Theoretical value 211.1117, test value 211.1122.
Embodiment 6
By 4 '-bromoacetophenones (40 mg), 3,5- dimethylphenyl boronic acid (45 mg), polycarbazole load nano palladium material (8 mg), Potassium phosphate (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-is added Pumping-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, Filtration of catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtain 3 ', 5 '-dimethyl -4- 4-acetylbiphenyls (yield 96%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 7.9 Hz, 2H), 7.66 (d, J = 7.9 Hz, 2H), 7.25 (d, J = 5.8 Hz, 3H), 7.05 (s, 1H), 2.63 (s, 3H), 2.39 (s, 6H).
13C NMR (151 MHz, CDCl3) δ 198.0, 146.3, 140.1, 138.7, 135.9, 130.1, 129.0, 127.4, 125.4, 26.9, 21.6.
High resolution mass spectrum data is as follows:
C16H17O [M + H]+Theoretical value 225.1274, test value 225.1274.
Embodiment 7
4 '-bromoacetophenones (40 mg), 4- methoxyphenylboronic acid (46 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-methoxyl group -4- 4-acetylbiphenyls (yield 98%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (600 MHz, CDCl3) δ 7.99 (d, J = 8.2 Hz, 2H), 7.63 (d, J = 8.2 Hz, 2H), 7.56 (d, J = 8.6 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H), 2.61 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.8, 160.1, 145.6, 135.5, 132.5, 129.2, 128.6, 126.8, 114.6, 55.6, 26.9.
High resolution mass spectrum data is as follows:
C15H15O2 [M + H]+Theoretical value 227.1067, test value 227.1067.
Embodiment 8
4 '-bromoacetophenones (40 mg), 4- tert-butylbenzeneboronic acid (53 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-tert-butyl -4- 4-acetylbiphenyls (yield 99%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 8.2 Hz, 2H), 7.59 (d, J = 8.2 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 2.64 (s, 3H), 1.37 (s, 9H).
13C NMR (151 MHz, CDCl3) δ 198.0, 151.7, 145.8, 137.1, 135.8, 129.1, 127.2, 127.1, 126.1, 34.9, 31.5, 26.9.
High resolution mass spectrum data is as follows:
C18H21O [M + H]+Theoretical value 253.1587, test value 253.1586.
Embodiment 9
4 '-bromoacetophenones (40 mg), 4- cyanophenylboronic acid (44 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphoric acid Potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-cyano -4- 4-acetylbiphenyls (yield 92%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (600 MHz, CDCl3) δ 8.05 (d, J = 8.1 Hz, 2H), 7.74 (d, J = 8.2 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 2.63 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.7, 144.5, 143.7, 137.1, 132.9, 129.3, 128.1, 127.7, 118.8, 112.1, 26.9.
High resolution mass spectrum data is as follows:
C15H12NO [M + H]+Theoretical value 222.0913, test value 222.0916.
Embodiment 10
4 '-bromoacetophenones (40 mg), 4- nitrobenzene boronic acid (50 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphoric acid Potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-nitro -4- 4-acetylbiphenyls (yield 91%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.6 Hz, 2H), 8.06 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.6 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H), 2.64 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.7, 147.9, 146.4, 143.3, 137.3, 129.4, 128.3, 127.8, 124.4, 27.0.
High resolution mass spectrum data is as follows:
C14H12NO3 [M + H]+Theoretical value 242.0812, test value 242.0813.
Embodiment 11
4 '-bromoacetophenones (40 mg), 4- formylphenylboronic acid (45 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-formoxyl -4- 4-acetylbiphenyls (yield 89%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 10.08 (s, 1H), 8.07 (d, J = 7.9 Hz, 2H), 7.99 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.8 Hz, 2H), 7.74 (d, J = 7.9 Hz, 2H), 2.66 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.8, 192.0, 146.0, 144.4, 136.9, 136.0, 130.6, 129.3, 128.1, 127.8, 27.0.
High resolution mass spectrum data is as follows:
C15H13O2 [M + H]+Theoretical value 225.0910, test value 225.0912.
Embodiment 12
4 '-bromoacetophenones (40 mg), 4- acetylbenzene boric acid (49 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4, -4 '-diacetyl biphenyl (yield 92%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 10.08 (s, 1H), 8.07 (d, J = 7.9 Hz, 2H), 7.99 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.8 Hz, 2H), 7.74 (d, J = 7.9 Hz, 2H), 2.66 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.8, 192.0, 146.0, 144.4, 136.9, 136.0, 130.6, 129.3, 128.1, 127.8, 27.0.
High resolution mass spectrum data is as follows:
C15H13O2 [M + H]+Theoretical value 225.0910, test value 225.0912.
Embodiment 13
4 '-bromoacetophenones (40 mg), 4- carbomethoxy phenyl boric acid (54 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 4 '-carbomethoxy -4- 4-acetylbiphenyls (yield 93%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.1 Hz, 2H), 8.06 (d, J = 8.1 Hz, 2H), 7.71 (t, J = 8.7 Hz, 4H), 3.95 (s, 3H), 2.65 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.9, 167.0, 144.7, 144.4, 136.7, 130.4, 130.0, 129.2, 127.7, 127.5, 52.5, 26.9.
High resolution mass spectrum data is as follows:
C16H15O3 [M + H]+Theoretical value 255.1016, test value 255.1015.
Embodiment 14
4 '-bromoacetophenones (40 mg), biphenylboronic acid (59 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain terphenyl ethyl ketone (yield 99%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.2 Hz, 2H), 7.77–7.69 (m, 6H), 7.65 (d, J = 7.5 Hz, 2H), 7.48 (t, J = 7.5 Hz, 2H), 7.38 (t, J = 7.2 Hz, 1H), 2.66 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.0, 145.5, 141.3, 140.6, 138.9, 136.1, 129.2, 129.1, 127.9, 127.9, 127.8, 127.3, 26.9.
High resolution mass spectrum data is as follows:
C20H17O [M + H]+Theoretical value 273.1274, test value 273.1277.
Embodiment 15
4 '-bromoacetophenones (40 mg), 1- naphthalene boronic acids (52 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 1 '-naphthalene -4- acetophenone (yield 98%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.0 Hz, 2H), 7.92 (t, J = 9.2 Hz, 2H), 7.85 (d, J = 8.4 Hz, 1H), 7.61 (d, J = 8.0 Hz, 2H), 7.58 – 7.49 (m, 2H), 7.45 (dd, J = 12.4, 7.2 Hz, 2H), 2.69 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.1, 146.0, 139.2, 136.2, 134.0, 131.4, 130.5, 128.6, 128.6, 128.5, 127.1, 126.6, 126.2, 125.8, 125.5, 26.9. HRMS (CI-TOF) m/z: [M + H]+ Calcd for C18H15O 247.1117; Found 247.1119.
High resolution mass spectrum data is as follows:
C18H15O [M + H]+Theoretical value 247.1117, test value 247.1119.
Embodiment 14
4 '-bromoacetophenones (40 mg), benzothiophene -2- boric acid (53 mg), polycarbazole are loaded into nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains 2 '-benzothiophene -4- acetophenones (yield 80%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.2 Hz, 2H), 7.85 (d, J = 7.6 Hz, 1H), 7.81 (d, J = 8.2 Hz, 3H), 7.68 (s, 1H), 7.37 (p, J = 7.1 Hz, 2H), 2.64 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.6, 142.8, 140.7, 140.1, 138.9, 136.6, 129.3, 126.6, 125.2, 125.0, 124.2, 122.6, 121.4, 26.9.
High resolution mass spectrum data is as follows:
C16H13OS [M + H]+Theoretical value 253.0682, test value 253.0681.
Embodiment 15
4- bromobenzaldehyde (37 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- biphenylcarboxaldehyde (yield 86%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 10.06 (s, 1H), 7.96 (d, J = 8.1 Hz, 2H), 7.76 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 7.4 Hz, 2H), 7.49 (t, J = 7.4 Hz, 2H), 7.42 (t, J = 7.2 Hz, 1H).
13C NMR (151 MHz, CDCl3) δ 192.2, 147.4, 139.9, 135.4, 130.5, 129.2, 128.7, 127.9, 127.6.
High resolution mass spectrum data is as follows:
C13H11O [M + H]+Theoretical value 183.0804, test value 183.0812.
Embodiment 16
4- bromobenzylcyanide (36 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- biphenylcarbonitriles (yield 95%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 7.4 Hz, 2H), 7.49 (t, J = 7.3 Hz, 2H), 7.46–7.38 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 145.9, 139.4, 132.8, 129.3, 128.9, 127.9, 127.4, 119.1, 111.1.
High resolution mass spectrum data is as follows:
C13H10N [M + H]+Theoretical value 180.0808, test value 180.0814.
Embodiment 17
4- bromo nitrobenzene (40 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- nitrobiphenyl (yield 90%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.5 Hz, 2H), 7.74 (d, J = 8.5 Hz, 2H), 7.63 (d, J = 7.3 Hz, 2H), 7.50 (t, J = 7.2 Hz, 2H), 7.47–7.40 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 147.9, 139.0, 129.4, 129.1, 128.0, 127.6, 124.3.
High resolution mass spectrum data is as follows:
C12H10NO2 [M + H]+Theoretical value 200.0706, test value 200.0710.
Embodiment 18
4- bromoanisole (37 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- biphenyl methyl ether (yield 84%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (600 MHz, CDCl3) δ 7.57 (dd, J = 8.2, 1.0 Hz, 2H), 7.55–7.52 (m, 2H), 7.43 (t, J = 7.7 Hz, 2H), 7.35–7.29 (m, 1H), 7.01–6.97 (m, 2H), 3.86 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 159.4, 141.0, 134.0, 128.9, 128.4, 126.9, 126.9, 114.4, 55.6.
High resolution mass spectrum data is as follows:
C13H13O [M + H]+Theoretical value 185.0961, test value 185.0966.
Embodiment 19
By the bromo- N of 4-, accelerine (40 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), phosphorus Sour potassium (64 mg) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, and 5 ml deionized waters, liquid nitrogen frozen-pumping is added Gas-inflated with nitrogen-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, mistake Catalyst, ethyl acetate washing catalyst are filtered out, ethyl acetate extracts filtrate, merges organic phase, through drying, mistake Filter is concentrated under reduced pressure, silica gel chromatography, obtains N, N- dimethylbenzidine (yield 82%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 7.6 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.25 (d, J = 10.4 Hz, 2H), 6.83 (d, J = 5.5 Hz, 2H), 2.98 (s, 6H).
13C NMR (151 MHz, CDCl3) δ 141.3, 128.9, 128.0, 126.5, 126.3, 113.9, 113.3, 41.1.
High resolution mass spectrum data is as follows:
C14H16N [M + H]+Theoretical value 198.1277, test value 198.1281.
Embodiment 20
2- bromonaphthalene (42 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), potassium phosphate (64 mg) are added Enter to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-solution is added Jelly is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 2- phenylnaphthalene (yield 91%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 7.96–7.85 (m, 3H), 7.75 (t, J = 8.9 Hz, 3H), 7.60–7.43 (m, 4H), 7.39 (t, J = 7.3 Hz, 1H).
13C NMR (151 MHz, CDCl3) δ 141.3, 138.8, 133.9, 132.8, 129.1, 128.6, 128.4, 127.9, 127.6, 127.6, 126.5, 126.1, 126.0, 125.8.
High resolution mass spectrum data is as follows:
C16H13 [M + H]+Theoretical value 205.1012, test value 205.1022.
Embodiment 21
4- bromopyridine (32 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 4- phenylpyridine (yield 79%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.66 (d, J = 5.3 Hz, 2H), 7.64 (d, J = 7.2 Hz, 2H), 7.50 (dd, J = 14.0, 6.6 Hz, 4H), 7.47 – 7.40 (m, 1H).
13C NMR (101 MHz, CDCl3) δ 150.2, 148.8, 138.2, 129.3, 127.2, 121.9.
High resolution mass spectrum data is as follows:
C11H10N [M + H]+Theoretical value 156.0808, test value 156.0818.
Embodiment 22
3- bromobenzothiophene (42 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 3- phenyl benzothiophene (yield 75%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 5.5 Hz, 2H), 7.63 (d, J = 7.5 Hz, 2H), 7.52 (t, J = 7.5 Hz, 2H), 7.43 (t, J = 8.7 Hz, 4H).
13C NMR (151 MHz, CDCl3) δ 140.9, 138.3, 138.1, 136.2, 128.9, 127.7, 124.6, 124.5, 123.6, 123.1.
High resolution mass spectrum data is as follows:
C14H11S [M + H]+Theoretical value 211.0576, test value 211.0581.
Embodiment 23
2- bromoquinoline (42 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 2- phenylchinoline (yield 86%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.20 (dd, J = 18.3, 8.3 Hz, 4H), 7.88 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.74 (t, J = 7.4 Hz, 1H), 7.58–7.44 (m, 4H).
13C NMR (101 MHz, CDCl3) δ 157.5, 148.3, 139.7, 137.2, 130.0, 129.8, 129.6, 129.1, 127.8, 127.7, 127.4, 126.6, 119.3.
High resolution mass spectrum data is as follows:
C15H12N [M + H]+Theoretical value 206.0964, test value 206.0976.
Embodiment 24
3- bromoquinoline (42 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 3- phenylchinoline (yield 86%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 9.19 (s, 1H), 8.29 (s, 1H), 8.16 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 7.1 Hz, 1H), 7.71 (d, J = 6.7 Hz, 3H), 7.58 (d, J = 6.4 Hz, 1H), 7.51 (d, J = 6.6 Hz, 2H), 7.44 (d, J = 6.5 Hz, 1H).
13C NMR (151 MHz, CDCl3) δ 150.0, 147.4, 138.0, 134.0, 133.5, 129.6, 129.3, 129.3, 128.3, 128.2, 128.2, 127.6, 127.2.
High resolution mass spectrum data is as follows:
C15H12N [M + H]+Theoretical value 206.0964, test value 206.0973.
Embodiment 25
4 '-chloro-acetophenones (31 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- 4-acetylbiphenyl (yield 82%), using existing polyphenyl and double oxazole (poly (benzoxadiazole)) Pd nano particle (Pd B-BO is loaded3), yield 8%.
The nuclear magnetic data of products therefrom is as follows:
1H NMR (600 MHz, CDCl3) δ 8.03 (t, J = 6.9 Hz, 2H), 7.68 (dd, J = 7.5, 6.3 Hz, 2H), 7.63 (dd, J = 10.2, 3.2 Hz, 2H), 7.52–7.44 (m, 2H), 7.43–7.37 (m, 1H), 2.64 (d, J = 5.5 Hz, 3H).
13C NMR (151 MHz, CDCl3) δ 197.9, 146.0, 140.1, 136.0, 129.1, 129.1, 128.4, 127.5, 127.4, 26.9.
High resolution mass spectrum data is as follows:
C14H13O [M + H]+Theoretical value 197.0961, test value 197.0961.
Embodiment 26
4 '-chlorobenzaldehydes (28 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- biphenylcarboxaldehyde (yield 76%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 10.06 (s, 1H), 7.96 (d, J = 8.1 Hz, 2H), 7.76 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 7.4 Hz, 2H), 7.49 (t, J = 7.4 Hz, 2H), 7.42 (t, J = 7.2 Hz, 1H).
13C NMR (151 MHz, CDCl3) δ 192.2, 147.4, 139.9, 135.4, 130.5, 129.2, 128.7, 127.9, 127.6.
High resolution mass spectrum data is as follows:
C13H11O [M + H]+Theoretical value 183.0804, test value 183.0812.
Embodiment 27
4- chlorobenzonitrile (27 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- biphenylcarbonitriles (yield 84%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 7.4 Hz, 2H), 7.49 (t, J = 7.3 Hz, 2H), 7.46–7.38 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 145.9, 139.4, 132.8, 129.3, 128.9, 127.9, 127.4, 119.1, 111.1.
High resolution mass spectrum data is as follows:
C13H10N [M + H]+Theoretical value 180.0808, test value 180.0814.
Embodiment 28
4- chloronitrobenzene (31 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 4- nitrobiphenyl (yield 81%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.5 Hz, 2H), 7.74 (d, J = 8.5 Hz, 2H), 7.63 (d, J = 7.3 Hz, 2H), 7.50 (t, J = 7.2 Hz, 2H), 7.47–7.40 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 147.9, 139.0, 129.4, 129.1, 128.0, 127.6, 124.3.
High resolution mass spectrum data is as follows:
C12H10NO2 [M + H]+Theoretical value 200.0706, test value 200.0710.
Embodiment 29
Chlorobenzene (22 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), potassium phosphate (64 mg) are added To equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-defrosting is added It is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, Filtration of catalyst, Ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, silicon Rubber column gel column chromatogram purification obtains biphenyl (yield 51%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 7.5 Hz, 4H), 7.45 (t, J = 7.5 Hz, 4H), 7.36 (t, J = 7.2 Hz, 2H).
13C NMR (151 MHz, cdcl3) δ 141.4, 129.0, 127.5, 127.4.HRMS (CI-TOF) m/z: [M + H]+ Calcd for C12H11 155.0855; Found 155.0852.
High resolution mass spectrum data is as follows:
C12H11 [M + H]+Theoretical value 155.0855, test value 155.0852.
Embodiment 30
4- chlorotoluene (25 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 4- methyl biphenyl (yield 35%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.5 Hz, 2H), 7.50 (d, J = 7.8 Hz, 2H), 7.42 (t, J = 7.5 Hz, 2H), 7.32 (t, J = 7.3 Hz, 1H), 7.25 (d, J = 8.3 Hz, 2H), 2.40 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 141.4, 138.6, 137.2, 129.7, 128.9, 127.2, 127.2, 21.3.
High resolution mass spectrum data is as follows:
C13H13 [M + H]+Theoretical value 169.1012, test value 169.1021.
Embodiment 31
By 2, '-chloro-acetophenone (31 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 2- acetyl biphenyl (yield 66%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.6 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 7.47–7.37 (m, 5H), 7.37 – 7.31 (m, 2H), 2.01 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 205.0, 141.0, 140.8, 140.6, 130.8, 130.4, 129.0, 128.8, 128.0, 128.0, 127.6, 30.6.
High resolution mass spectrum data is as follows:
C14H13O[M + H]+Theoretical value 197.0961, test value 197.0964.
Embodiment 32
By 3, '-chloro-acetophenone (31 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 3- acetyl biphenyl (yield 78%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.19 (s, 1H), 7.94 (d, J = 7.6 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.63 (d, J = 7.5 Hz, 2H), 7.54 (t, J = 7.7 Hz, 1H), 7.48 (t, J = 7.4 Hz, 2H), 7.39 (t, J = 7.2 Hz, 1H), 2.66 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 198.2, 141.9, 140.3, 137.8, 131.9, 129.2, 129.1, 128.0, 127.4, 127.1, 26.9.
High resolution mass spectrum data is as follows:
C14H13O[M + H]+Theoretical value 197.0961, test value 197.0961.
Embodiment 33
By 3, '-chlorobenzonitrile (27 mg), phenyl boric acid (37 mg), polycarbazole load nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 48 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 3- cyanobiphenyl (yield 80%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.55 (t, J = 8.5 Hz, 3H), 7.49 (t, J = 7.4 Hz, 2H), 7.45–7.38 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 142.6, 139.0, 131.6, 130.8, 129.7, 129.3, 128.5, 127.2, 119.0, 113.1.
High resolution mass spectrum data is as follows:
C13H10N[M + H]+Theoretical value 180.0808, test value 180.0808.
Embodiment 34
4- chloropyridine (23 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 4- phenylpyridine (yield 65%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.66 (d, J = 5.3 Hz, 2H), 7.64 (d, J = 7.2 Hz, 2H), 7.50 (dd, J = 14.0, 6.6 Hz, 4H), 7.47 – 7.40 (m, 1H).
13C NMR (101 MHz, CDCl3) δ 150.2, 148.8, 138.2, 129.3, 127.2, 121.9.
High resolution mass spectrum data is as follows:
C11H10N [M + H]+Theoretical value 156.0808, test value 156.0818.
Embodiment 35
3- chloropyridine (23 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 3- phenylpyridine (yield 70%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.85 (s, 1H), 8.59 (d, J = 4.0 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.58 (d, J = 7.4 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.41 (d, J = 7.2 Hz, 1H), 7.36 (dd, J = 7.7, 5.0 Hz, 1H).
13C NMR (101 MHz, CDCl3) δ 148.5, 148.4, 137.9, 136.8, 134.6, 129.2, 128.3, 127.3, 123.7.
High resolution mass spectrum data is as follows:
C11H10N [M + H]+Theoretical value 156.0808, test value 156.0815.
Embodiment 36
2- chloropyridine (23 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 2- phenylpyridine (yield 68%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 4.3 Hz, 1H), 8.00 (d, J = 7.4 Hz, 2H), 7.83 – 7.64 (m, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.42 (t, J = 7.2 Hz, 1H), 7.25 – 7.12 (m, 1H).
13C NMR (151 MHz, CDCl3) δ 157.6, 149.8, 139.5, 137.0, 129.2, 128.9, 127.1, 122.3, 120.8.
High resolution mass spectrum data is as follows:
C11H10N [M + H]+Theoretical value 156.0808, test value 156.0812.
Embodiment 37
3- bromobenzothiophene (34 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 3- phenyl benzothiophene (yield 68%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 5.5 Hz, 2H), 7.63 (d, J = 7.5 Hz, 2H), 7.52 (t, J = 7.5 Hz, 2H), 7.43 (t, J = 8.7 Hz, 4H).
13C NMR (151 MHz, CDCl3) δ 140.9, 138.3, 138.1, 136.2, 128.9, 127.7, 124.6, 124.5, 123.6, 123.1.
High resolution mass spectrum data is as follows:
C14H11S [M + H]+Theoretical value 211.0576, test value 211.0581.
Embodiment 38
2- chloroquinoline (32 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 2- phenylchinoline (yield 76%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 8.20 (dd, J = 18.3, 8.3 Hz, 4H), 7.88 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.74 (t, J = 7.4 Hz, 1H), 7.58–7.44 (m, 4H).
13C NMR (101 MHz, CDCl3) δ 157.5, 148.3, 139.7, 137.2, 130.0, 129.8, 129.6, 129.1, 127.8, 127.7, 127.4, 126.6, 119.3.
High resolution mass spectrum data is as follows:
C15H12N [M + H]+Theoretical value 206.0964, test value 206.0976.
Embodiment 39
3- chloroquinoline (32 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 mg) It is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-inflated with nitrogen-is added Defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove catalysis Agent, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, reduced pressure, Silica gel chromatography obtains 3- phenylchinoline (yield 80%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3) δ 9.19 (s, 1H), 8.29 (s, 1H), 8.16 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 7.1 Hz, 1H), 7.71 (d, J = 6.7 Hz, 3H), 7.58 (d, J = 6.4 Hz, 1H), 7.51 (d, J = 6.6 Hz, 2H), 7.44 (d, J = 6.5 Hz, 1H).
13C NMR (151 MHz, CDCl3) δ 150.0, 147.4, 138.0, 134.0, 133.5, 129.6, 129.3, 129.3, 128.3, 128.2, 128.2, 127.6, 127.2.
High resolution mass spectrum data is as follows:
C15H12N [M + H]+Theoretical value 206.0964, test value 206.0973.
Embodiment 40
2- chloro-quinoxaline (33 mg), phenyl boric acid (37 mg), polycarbazole are loaded into nano palladium material (8 mg), potassium phosphate (64 Mg it) is added to equipped in 10 ml crystal reaction tube of magnetic stir bar, 5 ml deionized waters, liquid nitrogen frozen-pumping-nitrogen charging is added Gas-defrosting is repeated three times, then under Blue-LED lamp, 12 h of closed room temperature reaction；After reaction, it is filtered to remove Catalyst, ethyl acetate washing catalyst, ethyl acetate extract filtrate, merge organic phase, through drying, filtering, decompression Concentration, silica gel chromatography, obtain 2- phenyl quinoxaline (yield 73%).
The nuclear magnetic data of products therefrom is as follows:
1H NMR (400 MHz, CDCl3, ppm) δ 9.34 (s, 1H), 8.25–8.10 (m, 4H), 7.83–7.72 (m, 2H), 7.56 (dq, J = 14.0, 6.9 Hz, 3H).
13C NMR (151 MHz, CDCl3, ppm) δ 152.1, 143.5, 142.5, 141.7, 137.0, 130.6, 130.4, 129.8, 129.8, 129.4, 129.3, 127.8.
High resolution mass spectrum data is as follows:
C14H11N2 [M + H]+Theoretical value 207.0917, test value 207.0932.
Presoma prepared by the present invention is polycarbazole material, and the nanoparticle of preparation is evenly distributed in polycarbazole substrate, 4.2 nm of average grain diameter or so, for photocatalysis using aromatic bromide or aromatic chlorides and fragrant boric acid as Material synthesis two Aryl compound has efficient catalytic efficiency.

Claims (10)

1. a kind of polycarbazole loads nano palladium material, which is characterized in that Technique of Nano Pd is distributed on carbazole polymer.
2. polycarbazole loads nano palladium material according to claim 1, which is characterized in that the load capacity of Technique of Nano Pd is 1.3 wt The wt of %~1.4 %；The average grain diameter of Technique of Nano Pd is 4~4.5 nm.
3. a kind of preparation method of polycarbazole load nano palladium material, includes the following steps: under inert gas, will contain Pd (OAc)2NaBH is added after being stirred with the aqueous solution of polycarbazole4Aqueous solution, then continue to be stirred to react, obtain poly- click Azoles loads nano palladium material.
4. the preparation method of polycarbazole load nano palladium material according to claim 3, which is characterized in that be stirred to react end Centrifugal treating afterwards, sediment are successively washed with water, ethyl alcohol, ether, are then dried in vacuo, and obtain polycarbazole load Technique of Nano Pd material Material.
5. the preparation method of polycarbazole load nano palladium material according to claim 3, which is characterized in that is be stirred stirs Mixing speed is 1000 rpms, and the time is 0.5 hour；The mixing speed being stirred to react is 1000 rpms, and the time is 4 small When；Polycarbazole loads in nano palladium material, and the load capacity of palladium is 1.3 wt of wt %~1.4 %；The inert gas is selected from nitrogen Any one in gas, argon gas.
6. polycarbazole loads nano palladium material and prepares in biaryl compound in photocatalysis aromatic halides and fragrant acid reaction Application；In the polycarbazole load nano palladium material, Technique of Nano Pd is distributed on carbazole polymer.
7. application according to claim 6, which is characterized in that polycarbazole loads in nano palladium material, and the load capacity of palladium is 1.3 wt of wt %~1.4 %；The average grain diameter of Technique of Nano Pd is 4~4.5 nm；The preparation method of polycarbazole load nano palladium material Include the following steps: under inert gas, Pd (OAc) will be contained2NaBH is added after being stirred with the aqueous solution of polycarbazole4's Aqueous solution then continues to be stirred to react, and obtains polycarbazole load nano palladium material.
8. application according to claim 6, which is characterized in that aromatic halides are aromatic bromide or aromatic chlorides； The aromatic bromide is selected from bromobenzene, alkyl substituted phenyl-bromide, alkoxy substituted phenyl-bromide, acetyl group substituted phenyl-bromide, formoxyl and replaces Any one in bromobenzene, cyano substituted phenyl-bromide, nitro substituted phenyl-bromide, naphthalene bromine and hetero-aromatic ring bromide；The aromatic chlorides Chlorobenzene, formoxyl is replaced to replace chlorobenzene, cyano that chlorobenzene, nitro is replaced to replace chlorobenzene, naphthalene chlorine and hetero-aromatic ring selected from chlorobenzene, acetyl group Any one in chloride；The fragrance boronic acid compounds are selected from phenyl boric acid, alkyl substituted benzene boric acid, alkoxy substituted boron Acid, acetyl group replace phenyl boric acid, formoxyl to replace phenyl boric acid, nitro that phenyl boric acid, cyano is replaced to replace phenyl boric acid, ester group substituted benzene Any one in boric acid, naphthalene boronic acids and heterocyclic boronic acids.
9. application according to claim 6, which is characterized in that aromatic halides and fragrant acid reaction prepare diarylide Object is closed to carry out in the presence of a base, in the presence of water, in nitrogen；Aromatic halides, fragrant boric acid, polycarbazole load Technique of Nano Pd material Expect, the amount ratio of alkali is 0.2 mol:0..3 mol:8 mg:0.3 mol.
10. application according to claim 9, which is characterized in that the alkali is selected from potassium phosphate；The solvent is water, N, N- Any one in dimethylformamide；The temperature of the reaction is room temperature；The illumination condition is that blue LED lamp shines condition； When the time of the reaction is 12~48.
CN201811314978.XA 2018-11-06 2018-11-06 Polycarbazole loaded nano-palladium material and preparation method and application thereof Active CN109317202B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811314978.XA CN109317202B (en) 2018-11-06 2018-11-06 Polycarbazole loaded nano-palladium material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811314978.XA CN109317202B (en) 2018-11-06 2018-11-06 Polycarbazole loaded nano-palladium material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109317202A true CN109317202A (en) 2019-02-12
CN109317202B CN109317202B (en) 2021-08-27

Family

ID=65259962

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811314978.XA Active CN109317202B (en) 2018-11-06 2018-11-06 Polycarbazole loaded nano-palladium material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109317202B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020097894A1 (en) * 2018-11-15 2020-05-22 南通纺织丝绸产业技术研究院 Polycarbazole-supported nano-palladium material, preparation method and application thereof
CN111530500A (en) * 2020-05-01 2020-08-14 苏州大学 Polycarbazole loaded cobalt hybrid material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491968A (en) * 2011-12-08 2012-06-13 大连理工大学 Method for preparing carbazolyl biaryl compound in aqueous phase
JP2014105208A (en) * 2012-11-30 2014-06-09 Ricoh Co Ltd N-arylcarbazole polymer
CN104959164A (en) * 2015-07-03 2015-10-07 湘潭大学 Polymer-nano metallic particle catalyst and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491968A (en) * 2011-12-08 2012-06-13 大连理工大学 Method for preparing carbazolyl biaryl compound in aqueous phase
JP2014105208A (en) * 2012-11-30 2014-06-09 Ricoh Co Ltd N-arylcarbazole polymer
CN104959164A (en) * 2015-07-03 2015-10-07 湘潭大学 Polymer-nano metallic particle catalyst and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FEIRAN CHEN ET AL.: "Synthesis of a Novel Cellulose Microencapsulated Palladium Nanoparticle and Its Catalytic Activities in Suzuki-Miyaura and Mizoroki-Heck Reactions", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *
HUI ZHOU ET AL.: "Palladium nanoparticles supported on a carbazole functionalized mesoporous organic polymer: synthesis and their application as efficient catalysts for the Suzuki-Miyaura cross coupling reaction", 《POLYMER CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020097894A1 (en) * 2018-11-15 2020-05-22 南通纺织丝绸产业技术研究院 Polycarbazole-supported nano-palladium material, preparation method and application thereof
CN111530500A (en) * 2020-05-01 2020-08-14 苏州大学 Polycarbazole loaded cobalt hybrid material and preparation method and application thereof
CN111530500B (en) * 2020-05-01 2022-07-19 苏州大学 Polycarbazole loaded cobalt hybrid material and preparation method and application thereof

Also Published As

Publication number Publication date
CN109317202B (en) 2021-08-27

Similar Documents

Publication Publication Date Title
Karimi et al. Ordered Mesoporous Organosilica with Ionic‐Liquid Framework: An Efficient and Reusable Support for the Palladium‐Catalyzed Suzuki–Miyaura Coupling Reaction in Water
Kumbhar et al. Palladium supported hybrid cellulose–aluminum oxide composite for Suzuki–Miyaura cross coupling reaction
Tamami et al. Palladium nanoparticles supported on modified crosslinked polyacrylamide containing phosphinite ligand: A novel and efficient heterogeneous catalyst for carbon–carbon cross-coupling reactions
Tamami et al. Palladium nanoparticles supported on poly (N-vinylpyrrolidone)-grafted silica as new recyclable catalyst for Heck cross-coupling reactions
Gholinejad et al. A novel polymer containing phosphorus–nitrogen ligands for stabilization of palladium nanoparticles: an efficient and recyclable catalyst for Suzuki and Sonogashira reactions in neat water
CA2419023C (en) Catalyst for aromatic c-o, c-n, and c-c bond formation
EP1308481A2 (en) Metal-mediated cross-coupling with ring-metalated porphyrins
Bakherad et al. Suzuki, Heck, and copper-free Sonogashira reactions catalyzed by 4-amino-5-methyl-3-thio-1, 2, 4-triazole-functionalized polystyrene resin-supported Pd (II) under aerobic conditions in water
CN109317202A (en) A kind of polycarbazole load nano palladium material and the preparation method and application thereof
Tandukar et al. N-heterocyclic carbene–palladium complex immobilized on silica nanoparticles: Recyclable catalyst for high yield Suzuki and Heck coupling reactions under mild conditions
Bulut et al. Suzuki cross-coupling reaction of aryl halides with arylboronic acids catalysed by Pd (II)-NaY zeolite
Kumar et al. Carbon-sulphur cross coupling reactions catalyzed by nickel-based coordination polymers based on metalloligands
CN1331914C (en) Method for synthesizing polymer of poly-triphenylamine
JP2008184418A (en) Palladium catalyst and method for producing biaryl-based compound or heterobiaryl-based compound using it
Pourmorteza et al. Cu (ii)–vitamin C-complex catalyzed photo-induced homocoupling reaction of aryl boronic acid in base-free and visible light conditions
Niknam et al. Synthesis of some new 1, 4-distyrylbenzenes using immobilized palladium nanoparticles on silica functionalized morpholine as a recyclable catalyst
Noori et al. Pd (0)-S-methylisothiourea grafted onto mesoporous MCM-41 and its application as heterogeneous and reusable nanocatalyst for the Suzuki, Stille and Heck cross coupling reactions
Iranpoor et al. Immobilized copper iodide on a porous organic polymer bearing P, N-ligation sites: a highly efficient heterogeneous catalyst for CO bond formation reaction
CN105968374B (en) A kind of copper (I) coordination polymer and its preparation method and application
Yang et al. Novel graphene-supported palladium complex catalyst with flexible-bridge-chains and its recycling carbon-carbon cross-coupling activity
CN114249902B (en) Preparation method and application of phenoxazine-based metal organic framework with visible light catalytic reduction C-F bond performance
KR101382530B1 (en) Catalyst comprising Pd supported on polymer-halloysite nanocomposite and method for preparing biaryl compounds using the catalyst
CN103058803A (en) Biphenyl compound and synthesis method for same
WO2020097894A1 (en) Polycarbazole-supported nano-palladium material, preparation method and application thereof
CN113968805B (en) Novel chiral thioether-sulfimide ligand and preparation method thereof

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