CN112588321A - Chitosan quaternary ammonium salt loaded dye photocatalyst and preparation method and application thereof - Google Patents
Chitosan quaternary ammonium salt loaded dye photocatalyst and preparation method and application thereof Download PDFInfo
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- CN112588321A CN112588321A CN202011378848.XA CN202011378848A CN112588321A CN 112588321 A CN112588321 A CN 112588321A CN 202011378848 A CN202011378848 A CN 202011378848A CN 112588321 A CN112588321 A CN 112588321A
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- quaternary ammonium
- ammonium salt
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 46
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000003480 eluent Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012434 nucleophilic reagent Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UWYZHKAOTLEWKK-UHFFFAOYSA-N tetrahydro-isoquinoline Natural products C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 5
- 229930187593 rose bengal Natural products 0.000 claims description 5
- 229940081623 rose bengal Drugs 0.000 claims description 5
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical group [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- -1 Ru (II) Chemical class 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229940125796 compound 3d Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
- C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a chitosan quaternary ammonium salt loaded dye photocatalyst and a preparation method and application thereof. The chitosan quaternary ammonium salt loaded dye photocatalyst is synthesized by one-step simple ion exchange by taking chitosan quaternary ammonium salt as a carrier. The chitosan quaternary ammonium salt loaded dye photocatalyst can catalyze dehydrogenation coupling reaction participated by various N-aryl tetrahydroisoquinolines under the condition of visible light radiation; the catalytic process is safe and simple to operate, the reaction condition is mild and efficient, the substrate range is wide, and the potential industrial application prospect is achieved; has good chemical stability, light stability and cycle stability.
Description
Technical Field
The invention relates to the technical field of heterogeneous photocatalysts, in particular to a chitosan quaternary ammonium salt loaded dye photocatalyst and a preparation method and application thereof.
Background
The light energy is a clean, cheap and easy-to-operate green energy source. Over a hundred years ago, italian chemist g.ciamicin pointed out: the solar energy with low energy consumption can replace high energy consumption energy, and becomes an important direction for the development of the future chemical industry. The photocatalysis technology directly utilizes solar energy, can complete chemical conversion at normal temperature and normal pressure, has no secondary pollution, has potential industrial application prospect, and is widely concerned by scientific research work.
At present, the photosensitizers widely used are mainly two main classes of metal complexes and organic dyes. The metal complex photosensitizer mainly comprises: complexes of transition metals such as Ru (II), Ir (III) and the like with small nitrogen-containing organic molecules, e.g. Ir (ppy)3、Ru(bpy)3Cl2·6H2O, and the like. The organic dye photosensitizer mainly comprises fluorescein, rhodamine, eosin, acridine salt and the like. The photocatalysts have higher molar absorptivity and longer excited state life under the irradiation of specific wavelength in a visible light region, show excellent catalytic activity in a homogeneous visible light catalytic system, but have some defects, such as difficult separation of the homogeneous photocatalyst from a product and difficult realization of recovery and recycling; metal complexes are expensive (Ir (ppy)3 1894€/g，Ru(bpy)3Cl2·6H2O131.5 {/g) and the synthesis steps are complicated; organic dyes, although relatively inexpensive (eosin. na)21.37 {/g) but difficult to degrade, destroy the ecological environment, etc.
In order to solve the problems, researchers propose a strategy of heterogenizing a homogeneous photocatalyst, and design a visible-light photocatalyst which has high catalytic activity and selectivity and is convenient to separate and recycle. The research shows that: a plurality of (silicon-based, graphene, synthetic polymer and metal organic framework) materials are used as carriers for preparing the heterogeneous visible light catalyst, realize organic synthesis reaction under the induction of visible light, and show excellent reaction activity.
Chitosan is a deacetylated product of chitin, is mainly distributed in shells of crustaceans such as shrimps, crabs and insects, is an important component in biomass resources, and is also an alkaline substance which is rarely contained in nature. The molecular structure of the chitosan contains a microscopic porous structure and a larger specific surface area, so that sufficient mass transfer area and load capacity can be provided; abundant functional groups (-OH, -NH)2) The material has nucleophilicity and electrophilicity, and can provide stronger coordination capacity or form a new chemical bond through chemical modification; meanwhile, the functional groups are easy to form intramolecular and intermolecular hydrogen bonds, so that the functional groups have good performanceMechanical strength, thermal stability and chemical stability, and has basic conditions as an excellent heterogeneous catalyst carrier material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a chitosan quaternary ammonium salt loaded dye photocatalyst.
The invention also aims to provide a preparation method of the chitosan quaternary ammonium salt supported dye photocatalyst.
The invention further aims to provide application of the chitosan quaternary ammonium salt loaded dye photocatalyst.
The purpose of the invention is realized by the following technical scheme: a chitosan quaternary ammonium salt loaded dye photocatalyst has a structural formula shown as a formula I:
in the formula I, A has a structure shown in a formula II or a formula III:
the invention provides a preparation method of the chitosan quaternary ammonium salt loaded dye photocatalyst, which comprises the following steps: slowly dripping the organic dye solution into the chitosan quaternary ammonium salt dispersion liquid, stirring after dripping, filtering, washing, and drying in vacuum to obtain the chitosan quaternary ammonium salt loaded dye photocatalyst.
The organic dye is preferably eosin Y or rose bengal.
The solvent of the organic dye solution is ethanol, and the concentration of the solution is 10-50 g/L.
The concentration of the chitosan quaternary ammonium salt dispersion liquid is 1-5 wt%.
The substitution degree of the chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt dispersion liquid is 85-95%.
The chitosan quaternary ammonium salt dispersion liquid is obtained by ultrasonic dispersion.
The stirring time is 24 h.
The eluent adopted by the washing is ethanol, and the washing is carried out until the eluent is colorless.
The vacuum drying is preferably carried out at 60 ℃ for 12 h.
The chitosan quaternary ammonium salt loaded dye photocatalyst is applied to photocatalytic organic synthesis.
The application method comprises the following steps: mixing the chitosan quaternary ammonium salt loaded dye photocatalyst, N-aryl tetrahydroisoquinoline or derivatives thereof with the structure shown in the formula IV, a nucleophilic reagent (Nu) and a reaction solvent, stirring and reacting under the irradiation of light, filtering, washing, combining leacheate, distilling under reduced pressure, separating and purifying to obtain a compound with the structure shown in the formula V; the reaction is a photocatalytic reaction, and has the following reaction formula:
in the formulas IV and V, R is one of hydrogen, methyl, methoxyl, chlorine and bromine.
The nucleophilic reagent is one of nitromethane, nitropropane, ethyl diazoacetate, dimethyl malonate and diethyl phosphite.
The reaction solvent is at least one of methanol, ethanol, acetone, acetonitrile, dichloromethane or dimethyl sulfoxide.
The dosage of the photocatalyst is (0.02-0.05) according to the molar ratio of the photocatalyst to the N-aryl tetrahydroisoquinoline or the derivative thereof: 1, calculating the mixture ratio.
The dosage of the nucleophilic reagent is (5-10) in the molar ratio of the nucleophilic reagent to the N-aryl tetrahydroisoquinoline or the derivative thereof: 1, calculating the mixture ratio.
The light irradiation time is 12-24 h.
The light source irradiated by the light is a blue LED lamp or a green LED lamp.
The lamp power of the blue LEDs is 12W, and the wavelength is 450 nm.
The power of the green LEDs is 12W, and the wavelength is 530 nm.
The washing is rinsing with ethyl acetate.
The separation and purification adopts column chromatography, and the granularity of the column chromatography is 200-300 meshes.
The eluent for column chromatography is (4-5) in volume ratio: 1 petroleum ether and dichloromethane.
Compared with the prior art, the invention has the following advantages and effects:
1. the chitosan quaternary ammonium salt loaded dye photocatalyst prepared by the invention can catalyze dehydrogenation coupling reaction participated by various N-aryl tetrahydroisoquinolines under the condition of visible light radiation; the catalytic process is safe and simple to operate, mild in reaction condition, high in efficiency, wide in substrate range and has potential industrial application prospect.
2. According to the invention, the cheap and easily-obtained chitosan quaternary ammonium salt is used as a carrier material, and the prepared dye-loaded photocatalyst has good chemical stability, light stability and cycling stability.
Drawings
FIG. 1 is an infrared image of the photocatalyst CS-RB after circulation.
FIG. 2 is a thermogram of photocatalyst CS-RB after recycling.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. Example 1 is the preparation of the chitosan quaternary ammonium salt supported dye photocatalyst of the present invention; examples 2 to 6 are applications of the chitosan quaternary ammonium salt supported dye photocatalyst in the field of photocatalytic reactions, and example 7 is a recovery and recycling experiment of the chitosan quaternary ammonium salt supported photocatalyst.
Example 1
Weighing chitosan quaternary ammonium salt (with the degree of substitution of 95 percent and the weight of 0.5g), adding the chitosan quaternary ammonium salt into 50mL of ethanol solution, and performing ultrasonic dispersion for 10 minutes to obtain chitosan quaternary ammonium salt dispersion liquid. Rose bengal (0.5g) was weighed into 10mL of ethanol solution and the resulting ethanol solution of rose bengal was slowly added dropwise to the chitosan quaternary ammonium salt dispersion. After the dropwise addition, the mixture is stirred and reacted for 24 hours at room temperature, filtered and washed by absolute ethyl alcohol until eluent is colorless, and red solid powder is obtained. And (3) placing the red solid powder at 60 ℃ for vacuum drying for 12 hours to obtain the chitosan quaternary ammonium salt loaded rose bengal photocatalyst, which is abbreviated as CS-RB.
Example 2
1a (0.2mmol), 2a nitromethane (2.0mmol), the photocatalyst CS-RB (20.0mg) prepared in example 1, and ethanol (3mL) were sequentially added to a 15mL reaction tube, and the reaction was stirred under irradiation with a green LED lamp (power 12W, wavelength 530nm) at room temperature for 12 hours (room temperature). After the reaction was completed, filtration was performed, rinsing with ethyl acetate (5mL × 3), eluates were combined, rotary-distilled under reduced pressure, and separation and purification by column chromatography (particle size 200 mesh) were performed using petroleum ether/dichloromethane (v/v ═ 5:1) as an eluent, to obtain a yellow liquid product 3a in a yield of 90%. The reaction process is as follows:
the structural characterization data for compound 3a is as follows:
1H NMR(400MHz,CDCl3)δ7.28–7.11(m,5H),6.98–6.96(d,J＝8.0Hz,2H),6.86–6.82(t,J＝7.2Hz,1H),5.56–5.52(t,J＝7.1Hz,1H),4.88–4.83(dd,J＝11.8,7.8Hz,1H),4.57–4.52(dd,J＝11.8,6.6Hz,1H),3.68–3.57(m,2H),3.11–3.03(m,1H),2.81–2.75(dt,J＝16.2,4.8Hz,1H)；13C NMR(100MHz,CDCl3)δ148.4,135.2,132.9,129.5,129.2,128.1,127.0,126.7,119.4,115.1,78.8,58.1,42.1,26.4.
example 3
1b (0.2mmol), 2a nitromethane (2.0mmol), the photocatalyst CS-RB (20.0mg) prepared in example 1 and ethanol (3mL) were sequentially added to a 15mL reaction tube, and the reaction was stirred under irradiation with a green LED lamp (power 12W, wavelength 530nm) at room temperature for 12 hours. After the reaction was completed, filtration was performed, rinsing with ethyl acetate (5mL × 3), the eluates were combined, rotary-distilled under reduced pressure, and separation and purification by column chromatography (particle size 200 mesh) using petroleum ether/dichloromethane (v/v ═ 5:1) as an eluent, to obtain a yellow liquid product 3b in 88% yield. The reaction process is as follows:
the structural characterization data for compound 3b is as follows:
1H NMR(400MHz,CDCl3)δ7.25–7.06(m,6H),6.88(d,J＝8.4Hz,2H),5.48(t,J＝7.2Hz,1H),4.86–4.80(m,1H),4.56–4.51(m,1H),3.66–3.53(m,2H),3.09–3.01(m,1H),2.78–2.71(m,1H),2.26(s,3H)；13C NMR(100MHz,CDCl3)δ146.3,135.3,132.9,129.9,129.2,129.0,127.9,126.9,126.6,115.9,78.8,58.3,42.3,26.2,20.3.
example 4
1c (0.2mmol), 2a nitromethane (2.0mmol), the photocatalyst CS-RB (10.0mg) prepared in example 1 and ethanol (3mL) were sequentially added to a 15mL reaction tube, and the reaction was stirred under irradiation with a green LED lamp (power 12W, wavelength 530nm) at room temperature for 12 hours. After the reaction was completed, filtration was performed, rinsing with ethyl acetate (5mL × 3), eluates were combined, rotary-distilled under reduced pressure, and separation and purification by column chromatography (particle size 300 mesh) were performed using petroleum ether/dichloromethane (v/v ═ 4:1) as an eluent, to obtain a yellow liquid product 3c in 80% yield. The reaction process is as follows:
the structural characterization data for compound 3c is as follows:
1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.4Hz,2H),7.28–7.23(m,3H),7.17–7.11(m,1H),6.83(d,J＝8.8Hz,2H),5.48(t,J＝7.2Hz,1H),4.85–4.80(m,1H),4.58–4.53(m,1H),3.64–3.58(m,2H),3.09–3.02(m,1H),2.80–2.76(m,1H)；13C NMR(100MHz,CDCl3)δ147.5,134.9,132.4,132.2,129.2,128.2,126.9,126.8,116.7,111.5,78.6,58.1,42.0,26.2.
example 5
1a (0.2mmol), 2b ethyl diazoacetate (1.0mmol), the photocatalyst CS-RB (10.0mg) prepared in example 1, and methylene chloride (3mL) were sequentially added to a 15mL reaction tube, and the reaction mixture was stirred under irradiation with a green LED lamp (power 12W, wavelength 530nm) at room temperature for 12 hours. After the reaction was completed, filtration was performed, rinsing with ethyl acetate (5mL × 3), the eluates were combined, rotary-distilled under reduced pressure, and separation and purification by column chromatography (particle size 300 mesh) using petroleum ether/dichloromethane (v/v ═ 4:1) as an eluent, to obtain a yellow liquid product 3d in a yield of 72%. The reaction process is as follows:
compound 3d structural characterization data are as follows:
1H NMR(400MHz,CDCl3)δ7.29–7.27(m,1H),7.20–7.17(m,2H),7.15–7.12(m,1H),7.09–7.07(d,J＝8.4Hz,2H),6.99–6.97(d,J＝8.4Hz,2H),5.72(s,1H),4.21–4.15(dd,J＝14.2,7.1Hz,2H),3.55–3.52(m,2H),3.02–2.84(m,2H),2.26–2.22(d,3H),1.28–1.19(t,3H)；13C NMR(100MHz,CDCl3)δ166.4,146.9,135.2,134.5,129.6,129.3,128.6,127.4,127.30,126.5,117.1,60.8,56.5,44.4,28.1,20.4,14.3.
example 6
1a (0.2mmol), 2b ethyl diazoacetate (1.0mmol), the photocatalyst CS-RB (10.0mg) prepared in example 1, and methylene chloride (3mL) were sequentially added to a 15mL reaction tube, and the reaction mixture was stirred under irradiation with a green LED lamp (power 12W, wavelength 530nm) at room temperature for 12 hours. After the reaction was completed, filtration was performed, rinsing with ethyl acetate (5mL × 3), eluates were combined, rotary-distilled under reduced pressure, and separation and purification by column chromatography (particle size 300 mesh) using petroleum ether/dichloromethane (v/v ═ 4:1) as an eluent, to obtain a yellow liquid product 3e in a yield of 78%. The reaction process is as follows:
the structural characterization data for compound 3e is as follows:
1H NMR(400MHz,CDCl3)δ7.29–7.27(m,1H),7.20–7.16(m,2H),7.15–7.11(m,1H),7.09–7.07(d,J＝8.3Hz,2H),6.99–6.97(d,J＝8.5Hz,2H),5.72(s,1H),4.21–4.14(dd,J＝14.2,7.1Hz,2H),3.55–3.52(m,2H),3.02–2.84(m,2H),2.27–2.22(d,3H),1.28–1.19(t,3H)；13C NMR(100MHz,CDCl3)δ166.3,146.8,135.1,134.5,129.6,129.4,128.6,127.5,127.3,126.5,117.1,60.8,56.5,44.5,28.0,20.4,14.3.
example 7
Adding 1 time equivalent of sym-trimethoxybenzene into the reaction system after the irradiation stirring reaction of the embodiment 2 as an internal standard, stirring and mixing for 10 minutes, centrifugally separating the photocatalyst, and passing a liquid phase layer1The reaction yield was tested by HNMR and the solid phase layer was rinsed with ethyl acetate (5 mL. times.3) and dried in vacuo at 60 ℃ for 12h and used directly for the next cycle. The cycle data are shown in Table 1. The photocatalyst CS-RB prepared in example 1 and the photocatalyst circulated in this example were examined by an infrared spectrometer and a thermogravimetric analyzer, and the results are shown in FIGS. 1 and 2.
Table 1 catalyst cycling test
Yield a was tested by 1HNMR with sym-trimethoxybenzene as internal standard.
The result proves that the chitosan quaternary ammonium salt loaded dye photocatalyst has good circulation stability, and can be recycled.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The chitosan quaternary ammonium salt loaded dye photocatalyst is characterized by having a structural formula shown as a formula I:
in the formula I, A has a structure shown in a formula II or a formula III:
2. the preparation method of the chitosan quaternary ammonium salt supported dye photocatalyst as claimed in claim 1, which is characterized by comprising the following steps: slowly dripping the organic dye solution into the chitosan quaternary ammonium salt dispersion liquid, stirring after dripping, filtering, washing, and drying in vacuum to obtain the chitosan quaternary ammonium salt loaded dye photocatalyst.
3. The method for preparing the dye-loaded quaternary ammonium salt chitosan photocatalyst according to claim 2,
the organic dye is eosin Y or rose bengal;
the solvent of the organic dye solution is ethanol, and the concentration of the solution is 10-50 g/L;
the concentration of the chitosan quaternary ammonium salt dispersion liquid is 1-5 wt%.
4. The method for preparing the dye-loaded quaternary ammonium salt chitosan photocatalyst according to claim 2 or 3,
the substitution degree of the chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt dispersion liquid is 85-95%;
the chitosan quaternary ammonium salt dispersion liquid is obtained by ultrasonic dispersion;
the stirring time is 24 hours;
the eluent adopted by the washing is ethanol, and the washing is carried out until the eluent is colorless;
the vacuum drying is carried out for 12 hours at the temperature of 60 ℃.
5. The application of the chitosan quaternary ammonium salt supported dye photocatalyst in photocatalytic organic synthesis according to claim 1.
6. The method for applying the chitosan quaternary ammonium salt loaded dye photocatalyst in photocatalytic organic synthesis, which is characterized by comprising the following steps: mixing the chitosan quaternary ammonium salt loaded dye photocatalyst, N-aryl tetrahydroisoquinoline or derivatives thereof with the structure shown in the formula IV, a nucleophilic reagent and a reaction solvent, stirring and reacting under the irradiation of light, filtering, washing, combining leacheate, distilling under reduced pressure, separating and purifying to obtain a compound with the structure shown in the formula V; the reaction formula is as follows:
in the formulas IV and V, R is one of hydrogen, methyl, methoxyl, chlorine and bromine.
7. The method of claim 6,
the nucleophilic reagent is one of nitromethane, nitropropane, ethyl diazoacetate, dimethyl malonate and diethyl phosphite;
the reaction solvent is at least one of methanol, ethanol, acetone, acetonitrile, dichloromethane or dimethyl sulfoxide;
the dosage of the photocatalyst is (0.02-0.05) according to the molar ratio of the photocatalyst to the N-aryl tetrahydroisoquinoline or the derivative thereof: 1, calculating the mixture ratio;
the dosage of the nucleophilic reagent is (5-10) in the molar ratio of the nucleophilic reagent to the N-aryl tetrahydroisoquinoline or the derivative thereof: 1, calculating the mixture ratio.
8. The method according to claim 6 or 7,
the light irradiation time is 12-24 h;
the light source irradiated by the light is a blue LED lamp or a green LED lamp.
9. The method of claim 8,
the power of the blue LEDs is 12W, and the wavelength is 450 nm;
the power of the green LEDs is 12W, and the wavelength is 53 nm.
10. The method according to claim 6 or 7,
the washing is leaching by adopting ethyl acetate;
column chromatography is adopted for separation and purification, and the granularity of the column chromatography is 200-300 meshes;
the eluent for column chromatography is (4-5) in volume ratio: 1 petroleum ether and dichloromethane.
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