CN106732783B - A kind of heterogeneous iridium pyridine complex visible light catalyst and the preparation method and application thereof - Google Patents
A kind of heterogeneous iridium pyridine complex visible light catalyst and the preparation method and application thereof Download PDFInfo
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- CN106732783B CN106732783B CN201611118718.6A CN201611118718A CN106732783B CN 106732783 B CN106732783 B CN 106732783B CN 201611118718 A CN201611118718 A CN 201611118718A CN 106732783 B CN106732783 B CN 106732783B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OXECIMIMUOWVJU-UHFFFAOYSA-N iridium;pyridine Chemical compound [Ir].C1=CC=NC=C1.C1=CC=NC=C1 OXECIMIMUOWVJU-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000011097 chromatography purification Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 150000007857 hydrazones Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000006352 cycloaddition reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- -1 stirrer is added Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 abstract 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FNKQXYHWGSIFBK-RPDRRWSUSA-N sapropterin Chemical compound N1=C(N)NC(=O)C2=C1NC[C@H]([C@@H](O)[C@@H](O)C)N2 FNKQXYHWGSIFBK-RPDRRWSUSA-N 0.000 description 2
- 229960004617 sapropterin Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/28—Nitrogen atoms
- C07D295/30—Nitrogen atoms non-acylated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of heterogeneous iridium pyridine complex visible light catalysts and the preparation method and application thereof, it is characterized by: using the copolymer of divinylbenzene and vinylpyridine as carrier, the catalyst that a certain amount of precious metal iridium complex is reaction has been coordinated on pyridine, in catalysis N, the cyclisation of accelerine and maleimide forms in 3,4-tetrahydroquinoline compounds and the perfluoroalkylation reaction of (E)-N- morpholine -1- phenyl imine and obtains good effect, and catalyst can reuse repeatedly, and keep catalytic activity.
Description
Technical field:
The invention belongs to field of material synthesis technology, in particular to a kind of heterogeneous iridium pyridine complex visible light catalysts
And the preparation method and application thereof.
Background technique:
The redox catalysis reaction of visible light-inducing is concentrated mainly on the composition catalyst of ruthenium (Ru) and iridium (Ir), this
Class catalyst can be efficiently used in the activation of inertia C-H key and the reaction of function dough.However, these transient metal complexes are made
Also there are many disadvantages for catalyst, limit its application in industrialization, such as at high cost, it is difficult to recycling and reuse
Deng.
Immobilized AlCl_3 catalyst has catalytic activity high compared with traditional homogeneous catalyst, can be recycled the performance recycled and
Widely paid close attention to.However, as photochemical catalyst, not only high specific surface area, but also need that light absorption cannot be hindered
Efficiency.Therefore, the inorganic carrier in part such as silica gel, aluminium oxide, active carbon etc. is difficult the carrier as photochemical catalyst.With nothing
Airborne body is compared, and organic polymer can be easily introduced into chelating site, and macromolecule load is prepared by simply copolymerization
Body.Active ligand pyridine and divinylbenzene (PDVB) are copolymerized by we, the porous copolymers material containing pyridine are prepared, so
Iridium coordination is got on again afterwards, novel supported iridium complex catalyst is prepared.Compared with general loaded catalyst, this
Kind has high stability with the heterogeneous catalysis that chemical bond form is prepared, and organic backbone ensure that and organic reactant
High-affinity.We are it was found that, this new catalyst can be urged very easily with high visible light catalysis activity
Change the product of the cycloaddition reaction tetrahydrobiopterin synthesis quinoline of tertiary amine and maleimide, while the perfluoroalkylation of hydrazone can also be catalyzed
Reaction.
Summary of the invention:
In view of the above-mentioned problems existing in the prior art, the first aspect of the present invention is designed to provide a kind of heterogeneous iridium pyrrole
Pyridine complex visible light catalyst, the catalyst can be applied to the catalysis reaction of two class visible light-inducings.
The technical solution adopted by the present invention is as follows:
A kind of heterogeneous iridium pyridine complex visible light catalyst, structure are shown below:
The second aspect of the present invention is designed to provide a kind of preparation method of aforementioned visible light catalyst, and feature exists
In, comprising the following steps:
(1), iridous chloride and phenylpyridine are dissolved in the mixed liquor of diethanol methyl ether and distilled water, stirrer are added,
Logical Ar protection, is heated to reflux at 120 DEG C, cooling after 15h, filtering, and product dry 12h under 60 DEG C of vacuum oven is obtained
To intermediate 1；
(2), vinylpyridine, divinylbenzene and ethyl acetate are stirred evenly, two isobutyl of initiator-azo is then added
Nitrile is put into reaction kettle after mixing evenly, and set temperature is 100 DEG C, after reacting 48h, is filtered, is obtained with different pyridine contents
Series polymer carrier 2 (2a-2d)；
(3), macromolecule carrier prepared by dried metal iridium catalyst and step (2) is dissolved in ethylene glycol, leads to Ar
Protection, setting temperature are 150 DEG C, and the 2h that flows back filters to obtain celadon solid powder after cooling, for 24 hours in 50 DEG C of vacuum drying, are obtained
To heterogeneous iridium pyridine complex visible light catalyst P (P1-P4).
Reaction equation of the present invention is as follows:
The third aspect of the present invention purpose is to provide a kind of aforementioned visible light catalyst and reacts in the catalysis of visible light-inducing
In application.
Visible light catalyst of the invention is mainly used for the catalysis reaction of two classes, and one is catalytic tertiary amines and maleimide
Cycloaddition reaction tetrahydrobiopterin synthesis quinoline product, another kind be catalyzed hydrazone perfluoroalkylation reaction, respectively it is as follows:
The cycloaddition reaction of catalytic tertiary amine and maleimide: by N, N- dimethyl-p-toluidine, N- methyl maleimide
Amine, it is seen that photochemical catalyst, N-Methyl pyrrolidone (NMP) are uniformly mixed, and are stirred to react 12h under 3W blue LED light photograph；Reaction
After the completion, reaction solution is poured into centrifuge tube, the catalyst isolated is subjected to recovery processing recycling, supernatant is poured into
In the water of 100mL, with 4 extractions of ethyl acetate point of 100mL, merge organic phase, with appropriate saturated common salt water washing, anhydrous sulphur
Sour sodium is dry, then carries out column Chromatographic purification and obtains final product.
It is catalyzed the perfluoroalkylation reaction of hydrazone: by (E)-N- morpholine -1- phenyl imine, C4F9I、Na2HPO4, visible light urges
Agent, DMF are uniformly mixed to be reacted at room temperature for 24 hours under the irradiation of 3W blue LED lamp, centrifugation recycling catalyst after reaction is completed,
Reaction solution is poured into water again, is extracted 4 times with the ethyl acetate of 100mL, merges organic phase, washed with appropriate saturated common salt
It washs, anhydrous sodium sulfate is dry, then carries out column Chromatographic purification and obtains final product.
Beneficial effects of the present invention are as follows:
In the present invention, metal complex is fixed on high molecular material in the form of chemical bond, and reaction can be with after terminating
The separation and recovery use of catalyst is carried out by simply filtering, therefore reaction system is more environmentally protective.And catalyst can
Recyclability can also greatly reduce reaction cost, make it possible to preferably using in industrial production.
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Detailed description of the invention:
Fig. 1 is the scanning electron microscope energy spectrum diagram (JSM-6360LV) of the catalyst P4 of preparation of the embodiment of the present invention；
Fig. 2 is the scanning electron microscope energy spectrum diagram (element and content) of the catalyst P4 of preparation of the embodiment of the present invention；
Fig. 3 is the scanning electron microscope energy spectrum diagram (Ir Elemental redistribution) of the catalyst P4 of preparation of the embodiment of the present invention；
Fig. 4 is the catalyst P4 of preparation of the embodiment of the present invention and the UV-visible absorption spectrum of polymer support；
Fig. 5 is the catalyst P4 of preparation of the embodiment of the present invention and the infrared spectrogram of polymer support.
Specific embodiment:
The synthesis of embodiment 1:tetrakis-2-phenylpyridine-bis- (μ-chloro)-diiridium (III)
8mmol (2.8g) iridous chloride and 18mmol (2.8g) phenylpyridine are dissolved in 300mL diethanol methyl ether and 100ml
In the mixed liquor of distilled water, stirrer is added, leads to Ar protection, is heated to reflux at 120 DEG C, cooling after 15h, filtering, product in
Dry 12h under 60 DEG C of vacuum oven, obtains intermediate 1, and yield is 70% (6g)；
Embodiment 2: the synthesis of divinylbenzene and vinylpyridine copolymer
By a certain amount of vinylpyridine, the ethyl acetate of divinylbenzene (20.0g, 0.154mol) and 200mL, stirring is equal
It is even, initiator-azodiisobutyronitrile of 0.01g is then added, is put into reaction kettle after mixing evenly, set temperature is 100 DEG C,
After reacting 48h, filters, obtain the series polymer carrier 2 (2a-2d) with different pyridine contents, yield 95%.
Embodiment 3: the synthesis of supported iridium complex
Dried metal iridium catalyst is weighed 0.76g and macromolecule carrier 2d 1.43g to be dissolved in 50mL ethylene glycol,
Logical Ar protection, setting temperature are 150 DEG C, and the 2h that flows back filters to obtain celadon solid powder after cooling, are dried in vacuo in 50 DEG C
For 24 hours, final catalyst P1-P4 (the Electronic Speculum characterization such as Fig. 1) of catalyst P4 is obtained.
Alternative embodiment:
By changing the inventory of vinylpyridine, the macromolecule carrier of available difference pyridine content, the quality of iridium
Percentage composition is quantified with ICP-AES.
Application Example 1:
By N, N- dimethyl-p-toluidine (2mmol), N- methylmaleimido (1mmol), P4 (1.2mol%), solvent
The N-Methyl pyrrolidone (NMP) of 20mL is uniformly mixed, and is stirred to react 12h under 3W blue LED light photograph.After the reaction was completed,
Reaction solution pours into centrifuge tube, the catalyst isolated is carried out recovery processing recycling, supernatant is poured into the water of 100mL
In, with 4 extractions of ethyl acetate point of 100mL, merge organic phase, with appropriate saturated common salt water washing, anhydrous sodium sulfate is dry,
Then it carries out column Chromatographic purification and obtains final product, yield 88%.m.p.207-208℃；1H NMR(400MHz,CDCl3)
δ 2.32 (s, 3H), 2.36 (s, 3H), 2.84 (s, 3H), 3.14 (dd, 1H, J=11.6,4.4Hz), 3.53-3.58 (m, 1H),
3.62 (dd, 1H, J=11.6,2.8Hz), 4.14 (d, 1H, J=9.6Hz), 6.77 (d, 1H, J=8.0Hz), 7.06 (dd, 1H,
), J=8.0,2.0Hz 7.13 (dd, 2H, J=8.4,2.0Hz), 7.23 (d, 2H, J=8.2Hz), 7.39 (d, 1H, J=
0.8Hz)。
Substrate is extended by we, and preferable effect is obtained under most of substituent group, as a result as shown in the table:
Application Example 2:
By (E)-N- morpholine -1- phenyl imine (1mmol), C4F9I(2mmol,2.0equiv),Na2HPO4(2mmol,
2.0equiv), P4 (0.01mmol, 1mol%), DMF (20mL) are uniformly mixed to be reacted at room temperature under the irradiation of 3W blue LED lamp
For 24 hours, centrifugation recycling catalyst after reaction is completed, then reaction solution is poured into water, it is extracted 4 times with the ethyl acetate of 100mL,
Merge organic phase, with appropriate saturated common salt water washing, anhydrous sodium sulfate is dry, then carries out column Chromatographic purification and obtains final production
Object, yield 86%.1H NMR(CDCl3, 400MHz) and δ (ppm) 2.98 (t, 4H, J=5.0Hz), 3.60 (t, 4H, J=
4.8Hz),7.34–7.37(m,2H),7.39–7.43(m,3H)。
Substrate we used other hydrazones as reaction, has been similarly obtained preferable yield, as a result as follows:
Application Example 3:
Obtained support type visible light catalyst ethanol washing will be centrifuged twice, dried, then put into embodiment 4
In reaction system, it is as shown in the table to reuse 5 results:
As can be seen from the table: the catalyst of recycling equally has very high catalytic activity, with catalysis number increase,
The yield of reaction is slightly reducing, it may be possible to have certain loss in the removal process of catalyst, lead to catalyst below
Amount deficiency caused by, use that catalyst can be stable 3 times.
Claims (4)
1. a kind of heterogeneous iridium pyridine complex visible light catalyst, structure are shown below:
。
2. a kind of preparation method of visible light catalyst described in claim 1, which comprises the following steps:
(1), iridous chloride and phenylpyridine are dissolved in the mixed liquor of diethanol methyl ether and distilled water, stirrer is added, lead to Ar
Protection, is heated to reflux at 120 DEG C, cooling after 15h, filtering, product dry 12h under 60 DEG C of vacuum oven, obtains
Mesosome is as shown in Equation 1；
Formula 1；
(2), vinylpyridine, divinylbenzene and ethyl acetate are stirred evenly, initiator-azodiisobutyronitrile is then added, stirs
It is put into reaction kettle after mixing uniformly, set temperature is 100 DEG C, after reacting 48h, filters, obtains the series with different pyridine contents
Polymer support is as shown in Equation 2；
Formula 2；
(3), polymer support prepared by dried intermediate and step (2) is dissolved in ethylene glycol, leads to Ar protection, setting temperature
Degree is 150 DEG C, and the 2h that flows back filters to obtain celadon solid powder after cooling, for 24 hours in 50 DEG C of vacuum drying, obtains heterogeneous iridium pyrrole
Pyridine complex visible light catalyst.
3. heterogeneous iridium pyridine complex visible light catalyst described in a kind of claim 1 is in catalytic tertiary amine and maleimide
Application in cycloaddition reaction, it is characterised in that: by N, N- dimethyl-p-toluidine, N- methylmaleimido, it is seen that light is urged
Agent, N-Methyl pyrrolidone are uniformly mixed, and are stirred to react 12h under 3W blue LED light photograph；After the reaction was completed, reaction solution
It pours into centrifuge tube, the catalyst isolated is subjected to recovery processing recycling, supernatant is poured into the water of 100mL, is used
4 extractions of the ethyl acetate of 100mL point, merge organic phase, and with appropriate saturated common salt water washing, anhydrous sodium sulfate is dry, then
It carries out column Chromatographic purification and obtains final product.
4. heterogeneous iridium pyridine complex visible light catalyst described in a kind of claim 1 is in the perfluoroalkylation reaction of catalysis hydrazone
In application, it is characterised in that: by (E)-N- morpholine -1- phenyl imine, C4F9I、Na2HPO4, visible light catalyst, DMF it is mixed
Conjunction uniformly reacts at room temperature under the irradiation of 3W blue LED lamp for 24 hours, centrifugation recycling catalyst after reaction is completed, then reaction solution
It is poured into water, is extracted 4 times with the ethyl acetate of 100mL, merge organic phase, with appropriate saturated common salt water washing, anhydrous slufuric acid
Sodium is dry, then carries out column Chromatographic purification and obtains final product.
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| CN103965449A (en) * | 2013-01-30 | 2014-08-06 | 宁波大学 | Iridium-containing optical-function polymer and preparation method thereof |
| CN104961773A (en) * | 2015-07-16 | 2015-10-07 | 江西师范大学 | Synthesis of cyclic metal iridium coordination compound and application of cyclic metal iridium coordination compound in preparing polymer white-light devices |
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| CN103965449A (en) * | 2013-01-30 | 2014-08-06 | 宁波大学 | Iridium-containing optical-function polymer and preparation method thereof |
| CN104961773A (en) * | 2015-07-16 | 2015-10-07 | 江西师范大学 | Synthesis of cyclic metal iridium coordination compound and application of cyclic metal iridium coordination compound in preparing polymer white-light devices |
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