CN106732783A - A kind of heterogeneous iridium pyridine complex visible light catalyst and preparation method and application - Google Patents
A kind of heterogeneous iridium pyridine complex visible light catalyst and preparation method and application Download PDFInfo
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- CN106732783A CN106732783A CN201611118718.6A CN201611118718A CN106732783A CN 106732783 A CN106732783 A CN 106732783A CN 201611118718 A CN201611118718 A CN 201611118718A CN 106732783 A CN106732783 A CN 106732783A
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- catalyst
- reaction
- visible light
- light catalyst
- iridium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 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 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 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
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 phenyl imine Chemical class 0.000 claims abstract description 5
- 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
- 238000003756 stirring Methods 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 230000004224 protection Effects 0.000 claims description 7
- 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
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 5
- 150000007857 hydrazones Chemical class 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006352 cycloaddition reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 238000001291 vacuum drying Methods 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical class CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract 1
- 150000002780 morpholines Chemical class 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
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 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
- 0 *C(c1ccccc1)=NN1CCOCC1 Chemical compound *C(c1ccccc1)=NN1CCOCC1 0.000 description 1
- FFFLJGBVTDTVCP-ZRDIBKRKSA-N C(COCC1)N1/N=C/c1ccccc1 Chemical compound C(COCC1)N1/N=C/c1ccccc1 FFFLJGBVTDTVCP-ZRDIBKRKSA-N 0.000 description 1
- 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 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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000000034 method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of heterogeneous iridium pyridine complex visible light catalyst and preparation method and application, it is characterised in that：Copolymer with divinylbenzene and vinylpyridine is 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 N dimethylanilines and maleimide obtains good effect in forming the perfluoroalkylation reaction of 3,4-tetrahydroquinoline compounds and the phenyl imine of (E) N morpholines 1, and catalyst can be reused repeatedly, and keep catalysis activity.
Description
Technical field：
The invention belongs to field of material synthesis technology, a kind of heterogeneous iridium pyridine complex visible light catalyst is specifically referred to
And preparation method and application.
Background technology：
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 efficiently used in the activation of inertia C-H keys and the reaction of function dough.However, these transient metal complexes are made
Also there are many shortcomings for catalyst, limit its application in industrialization, such as high cost, it is difficult to reclaim and reuse
Deng.
Immobilized AlCl_3 catalyst compared with traditional homogeneous catalyst have catalysis activity it is high, the performance of recyclable recycling and
Widely paid close attention to.However, as photochemical catalyst, not only specific surface area high, and also need to that light absorbs can not be hindered
Efficiency.Therefore, the inorganic carrier in part such as silica gel, aluminum oxide, activated carbon etc. is difficult to turn into the carrier of photochemical catalyst.With nothing
Airborne body phase ratio, organic polymer can be easily introduced into chelating site, and prepare macromolecule load by simple copolymerization
Body.Active ligand pyridine and divinylbenzene (PDVB) copolymerization are prepared the porous copolymers material containing pyridine, so by us
Iridium coordination is got on again afterwards, novel supported iridium complex catalyst is prepared.Compared with general loaded catalyst, this
Planting the heterogeneous catalysis prepared with chemical bond form has high stability, and organic backbone ensure that and organic reactant
High-affinity.We can be very easily urged it was found that, this new catalyst has visible light catalysis activity high
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.
The content of the invention：
In view of the above-mentioned problems existing in the prior art, the first aspect of the present invention purpose is to provide a kind of heterogeneous iridium pyrrole
Pyridine complex visible light catalyst, the catalyst can be applied to the catalytic reaction of two class visible light-inducings.
The technical scheme that the present invention takes is as follows：
A kind of heterogeneous iridium pyridine complex visible light catalyst, its structure is shown below：
The second aspect of the present invention purpose is to provide a kind of preparation method of foregoing visible light catalyst, and its 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 is added,
Logical Ar protections, are heated to reflux at 120 DEG C, and after 15h, cooling, filtering, product is obtained in 12h is dried under 60 DEG C of vacuum drying chamber
To intermediate 1；
(2), by vinylpyridine, divinylbenzene and ethyl acetate stir, and are subsequently adding the isobutyl of initiator-azo two
Nitrile, is put into reactor after stirring, and design temperature is 100 DEG C, and after reaction 48h, suction filtration 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, it is 150 DEG C to set temperature, and flowed back 2h, and after cooling, suction filtration obtains celadon solid powder, and 24h is vacuum dried in 50 DEG C, is 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 catalytic reaction of foregoing visible light catalyst in visible light-inducing
In application.
Visible light catalyst of the invention, is mainly used in two class catalytic reactions, and one kind is catalytic tertiary amine 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-toluidines, N- methyl maleimides
Amine, it is seen that photochemical catalyst, 1-METHYLPYRROLIDONE (NMP) is well mixed, the stirring reaction 12h under 3W blue LED lights photograph；Reaction
After the completion of, reaction solution is poured into centrifuge tube, the catalyst that will be isolated carries out recycling recycling, and 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 dried, and is then carried out column chromatography purification and is obtained final product.
It is catalyzed the perfluoroalkylation reaction of hydrazone：By (E)-N- morpholine -1- phenyl imines, C4F9I、Na2HPO4, visible ray urges
Agent, DMF are well mixed the room temperature reaction 24h under the irradiation of 3W blue LED lamps, and reaction is centrifuged after completing and reclaims catalyst,
Reaction solution is poured into water again, is extracted 4 times with the ethyl acetate of 100mL, merge organic phase, washed with appropriate saturated common salt
Wash, anhydrous sodium sulfate drying, then carry out column chromatography purification and obtain final product.
Beneficial effects of the present invention are as follows：
In the present invention, metal complex is fixed on macromolecular material in the form of chemical bond, and reaction can be with after terminating
The separation and recovery for carrying out catalyst by simple filtering is used, therefore reaction system compares environmental protection.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.
Brief description of the drawings：
Fig. 1 is the ESEM energy spectrum diagram (JSM-6360LV) of catalyst P4 prepared by the embodiment of the present invention；
Fig. 2 is the ESEM energy spectrum diagram (element and content) of catalyst P4 prepared by the embodiment of the present invention；
Fig. 3 is the ESEM energy spectrum diagram (Ir Elemental redistributions) of catalyst P4 prepared by the embodiment of the present invention；
Fig. 4 is the UV-visible absorption spectrum of catalyst P4 prepared by the embodiment of the present invention and polymer support；
Fig. 5 is the infrared spectrogram of catalyst P4 prepared by the embodiment of the present invention and polymer support.
Specific embodiment：
Embodiment 1：The synthesis of tetrakis-2-phenylpyridine-bis- (μ-chloro)-diiridium (III)
8mmol (2.8g) iridous chlorides and 18mmol (2.8g) phenylpyridine are dissolved in 300mL diethanols methyl ether and 100ml
In the mixed liquor of distilled water, add stirrer, lead to Ar protection, be heated to reflux at 120 DEG C, after 15h, cooling, filtering, product in
12h is dried under 60 DEG C of vacuum drying chamber, intermediate 1 is obtained, 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, the initiator-azodiisobutyronitrile of 0.01g is subsequently adding, it is put into reactor after stirring, design temperature is 100 DEG C,
After reaction 48h, suction filtration obtains the series polymer carrier 2 (2a-2d) with different pyridine contents, and yield is 95%.
Embodiment 3：The synthesis of supported iridium complex
Dried metal iridium catalyst is weighed into 0.76g and macromolecule carrier 2d 1.43g to be dissolved in 50mL ethylene glycol,
Logical Ar protections, it is 150 DEG C to set temperature, and flow back 2h, and after cooling, suction filtration obtains celadon solid powder, in 50 DEG C of vacuum drying
24h, obtains final catalyst P1-P4 (Electronic Speculum of catalyst P4 characterizes such as Fig. 1).
Alternative embodiment：
By changing the inventory of vinylpyridine, the macromolecule carrier of different pyridine contents, the quality of iridium can be obtained
Percentage composition is quantified with ICP-AES.
Application Example 1：
By N, N- dimethyl-p-toluidines (2mmol), N- methylmaleimidos (1mmol), P4 (1.2mol%), solvent
The 1-METHYLPYRROLIDONE (NMP) of 20mL is well mixed, the stirring reaction 12h under 3W blue LED lights photograph.After the completion of reaction,
Reaction solution is poured into centrifuge tube, and the catalyst that will be isolated carries out recycling recycling, and supernatant is poured into the water of 100mL
In, with points of 4 times extractions of ethyl acetate of 100mL, merge organic phase, with appropriate saturated common salt water washing, anhydrous sodium sulfate drying,
Then carry out column chromatography purification and obtain final product, yield is 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)。
Be extended for substrate by we, and preferable effect is obtained under major part substitution base, as a result as shown in the table：
Application Example 2：
By (E)-N- morpholine -1- phenyl imines (1mmol), C4F9I(2mmol,2.0equiv),Na2HPO4(2mmol,
2.0equiv), P4 (0.01mmol, 1mol%), DMF (20mL) is well mixed the room temperature reaction under the irradiation of 3W blue LED lamps
24h, reaction is centrifuged after completing and reclaims catalyst, then reaction solution is poured into water, is extracted 4 times with the ethyl acetate of 100mL,
Merge organic phase, with appropriate saturated common salt water washing, then anhydrous sodium sulfate drying carries out column chromatography purification and obtain final product
Thing, yield is 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)。
We used other hydrazones as the substrate of reaction, preferable yield is similarly obtained, it is as a result as follows：
Application Example 3：
Support type visible light catalyst obtained by centrifugation is washed twice with ethanol, is dried, then put into embodiment 4
In reaction system, the result for reusing 5 times is as shown in the table：
As can be seen from the table：The catalyst of recovery equally has catalysis activity very high, with the increase of catalysis number of times,
The yield of reaction is slightly being reduced, it may be possible to is had certain loss in the middle of the removal process of catalyst, is caused catalyst below
Amount it is not enough caused, the use that catalyst can be stablized 3 times.
Claims (4)
1. a kind of heterogeneous iridium pyridine complex visible light catalyst, its structure is shown below：
2. the preparation method of visible light catalyst described in a kind of claim 1, it is characterised in that comprise 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, after 15h, cooling, filtering, product in drying 12h under 60 DEG C of vacuum drying chamber, in obtaining
Mesosome is as shown in Equation 1；
(2), by vinylpyridine, divinylbenzene and ethyl acetate stir, and are subsequently adding initiator-azodiisobutyronitrile, stir
It is put into reactor after mixing uniformly, design temperature is 100 DEG C, after reaction 48h, suction filtration obtains the series with different pyridine contents
Polymer support is as shown in Equation 2；
(3), macromolecule carrier prepared by dried metal iridium catalyst and step (2) is dissolved in ethylene glycol, leads to Ar protections,
It is 150 DEG C to set temperature, and flowed back 2h, and after cooling, suction filtration obtains celadon solid powder, and 24h is vacuum dried in 50 DEG C, obtains non-equal
Phase iridium pyridine complex visible light catalyst.
3. the visible light catalyst described in a kind of claim 1, for catalytic tertiary amine and the cycloaddition reaction of maleimide：Will
N, N- dimethyl-p-toluidine, N- methylmaleimidos, it is seen that photochemical catalyst, 1-METHYLPYRROLIDONE are well mixed, in 3W
Blue LED light shines lower stirring reaction 12h；After the completion of reaction, reaction solution is poured into centrifuge tube, the catalyst that will be isolated is carried out
Recycling is recycled, and supernatant is poured into the water of 100mL, with 4 extractions of ethyl acetate point of 100mL, merges organic phase,
With appropriate saturated common salt water washing, then anhydrous sodium sulfate drying carries out column chromatography purification and obtains final product.
4. the visible light catalyst described in a kind of claim 1, the perfluoroalkylation reaction for being catalyzed hydrazone：By (E)-N-
Quinoline -1- phenyl imines, C4F9I、Na2HPO4, visible light catalyst, DMF be well mixed the room temperature under the irradiation of 3W blue LED lamps
Reaction 24h, reaction is centrifuged after completing and reclaims catalyst, then reaction solution is poured into water, is extracted with the ethyl acetate of 100mL
4 times, merge organic phase, with appropriate saturated common salt water washing, then anhydrous sodium sulfate drying carries out column chromatography purification and obtain final
Product.
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| CN108435255A (en) * | 2018-04-09 | 2018-08-24 | 陕西理工大学 | A kind of monatomic catalyst of iridium and the preparation method and application thereof |
| CN112495439A (en) * | 2020-11-23 | 2021-03-16 | 万华化学集团股份有限公司 | Photocatalytic catalyst, preparation method thereof and preparation method of vitamin A palmitate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491989A (en) * | 2011-11-26 | 2012-06-13 | 南京大学 | Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491989A (en) * | 2011-11-26 | 2012-06-13 | 南京大学 | Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435255A (en) * | 2018-04-09 | 2018-08-24 | 陕西理工大学 | A kind of monatomic catalyst of iridium and the preparation method and application thereof |
| CN112495439A (en) * | 2020-11-23 | 2021-03-16 | 万华化学集团股份有限公司 | Photocatalytic catalyst, preparation method thereof and preparation method of vitamin A palmitate |
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