CN109134881A - A kind of preparation method and application based on copper complex heterogeneous catalysis material - Google Patents
A kind of preparation method and application based on copper complex heterogeneous catalysis material Download PDFInfo
- Publication number
- CN109134881A CN109134881A CN201811085640.1A CN201811085640A CN109134881A CN 109134881 A CN109134881 A CN 109134881A CN 201811085640 A CN201811085640 A CN 201811085640A CN 109134881 A CN109134881 A CN 109134881A
- Authority
- CN
- China
- Prior art keywords
- alkynyl
- copper complex
- triazole derivatives
- application
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method and applications based on copper complex heterogeneous catalysis material, have constructed crystalline state MOF material [Cu by the self assembly with copper ion using TPB as organic ligand3I3(TPB)2]n(Cu-MOF).The catalyst of preparation heterogeneous catalysis at room temperature catalyzed three-component series connection cycloaddition reaction synthesis 5- alkynyl -1,2,3- triazole derivatives application.MOF material of the invention can be prepared by common hydro-thermal method technique, preparation method is simple, to catalyze and synthesize 5- alkynyl -1,2,3- triazole derivatives provide new selection, complex material application value has been expanded simultaneously, the stability of heterogeneous catalysis obtained is preferable, and is catalyzing and synthesizing 5- alkynyl -1,2, good activity is shown in the experiment of 3- triazole derivatives, shows that there is very high catalytic activity and the feature of environmental protection.
Description
Technical field
The present invention relates to heterogeneous catalysis field of material technology, and in particular to based on copper complex heterogeneous catalysis material
Preparation method and application.
Background technique
21 century makes rapid progress with industrialized continuous development, human society, and energy shortage and environmental pollution are
The ultimate challenge faced as human health, the ecological balance and socio-economic development.Most of substance of today's society is all logical
Cross catalysis reaction and produce, thus, the catalysis material of Development of Novel be realize sustainable development effective way.Therefore, it makes
Standby novel environmental-friendly, efficient the catalyst environmental pressure and realization social sustainable development increasingly serious to alleviation China
It is significant.
Crystalline state porous organo-metallic skeleton compound (MOFs) material has both inorganic unit and organo units advantage in one
Body becomes a kind of new catalytic material that academia nearly ten years widely attractes attention.The porous MOFs material of crystalline state has and zeolites
As structure and feature tended in adsorption reaction substrate to duct first when being catalyzed organic reaction, then by metal
The heart participates in catalysis and generates the selectivity such as special chemistry, size, solid by its specific cellular structure.Secondly, crystalline state is porous
MOFs material can play the centrical synergistic effect of polygamy, to realize that tandem reaction or collaboration are anti-by " treating different things alike "
It answers.The porous MOFs catalyst of crystalline state has high catalytic efficiency, selective to substrate, the features such as can recycling, is developing
Efficient catalytic material has vast potential for future development.
Summary of the invention
The invention proposes a kind of preparation method and application in copper complex heterogeneous catalysis material, the present invention utilizes N,
N, N-tris (3-pyridinyl) -1,3,5-benzenetricarboxamide(TPB) be used as organic ligand, by with copper from
The self assembly of son, has constructed a kind of crystalline state MOF material [Cu with good heterogeneous catalysis performance3I3(TPB)2]n(Cu-
MOF).
It realizes the technical scheme is that a kind of preparation method based on copper complex heterogeneous catalysis material, step
It is as follows:
(a) cuprous iodide is dissolved in acetonitrile, stirring at normal temperature 30-50min obtains mixed solution；
(b) by the mixed solution of the acetonitrile solution dropwise of TPB ligand to step (a), stirring and dissolving；
(c) step (b) reaction solution is placed in closed reactor, 100-120 DEG C of hydro-thermal reaction 60-80h；
(d) after reacting, room temperature is down to the rate of 5 DEG C/h, yellowish crystal is obtained, is successively washed with distilled water and acetonitrile, it is dry,
Obtain target product copper complex.
The molar ratio of cuprous iodide and step (b) TPB ligand is 1:(0.3-0.6 in the step (a)).
Application of the copper complex in synthesis 5- alkynyl -1,2,3- triazole derivatives.
Application of the copper complex in synthesis 5- alkynyl -1,2,3- triazole derivatives, steps are as follows:
(1) container is placed in using benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl, fragrant alkynes, Anhydrous potassium carbonate as reaction substrate
In；
(2) catalyst copper complex is added into the reaction solution of step (1), reaction obtains 5- alkynyl -1,2, tri- nitrogen of 3- at room temperature
Zole derivatives.
Benzyl azide in the step (1), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl, fragrant alkynes, Anhydrous potassium carbonate molar ratio be
1:(1-1.5): (1.3-2): (2-4).
It is described fragrance alkynes structural formula be, wherein R be H, F, Me, NC(cyano), Ph.
The structural formula of the 5- alkynyl -1,2,3- triazole derivatives is, wherein R be H, F, Me,
NC(cyano), Ph.
The molar ratio of catalyst and benzyl azide in step (1) is 0.05:1 in the step (2).
The reaction time is 8-10h in the step (2).
The beneficial effects of the present invention are: catalyst of the invention can be prepared by common hydro-thermal method technique, preparation side
Method is simple and easy, and to catalyze and synthesize 5- alkynyl -1,2,3- triazole derivatives provide new selection, while having expanded crystalline state
The application value of MOF material.Catalyst material of the invention is in catalyzing and synthesizing the experiment of 5- alkynyl -1,2,3- triazole derivatives
Good activity is shown, shows that there is very high catalytic activity and the feature of environmental protection.Catalyst material stability of the invention is good,
Stablize in 300 DEG C or less holdings, and the crystal state that can be remained intact in entire catalytic process, is beaten for circulation and stress recycling
Lower basis.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is TPB ligand molecular formula of the present invention.
Fig. 2 is the crystal structure figure of Cu-MOF material.
Fig. 3 is the thermogravimetric analysis figure of Cu-MOF material.
Fig. 4-8 is the product nuclear-magnetism figure of three component of Cu-MOF catalyst series connection cycloaddition reaction.
Fig. 9 is Cu-MOF catalyst circulation experiment test chart.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
The preparation of Cu-MOF catalyst:
(1) CuI (0.019 gram, 0.1mmol) is added in 25mL polytetrafluoro reaction kettle, 3mL acetonitrile is added, room temperature is protected from light magnetic
After power stirs 40min；
(2) by N, N, N-tris (3-pyridinyl) -1,3,5-benzenetricarboxamide(TPB) ligand (0.017
Gram, 0.03mmol) stirring and dissolving in 4mL acetonitrile and is added dropwise in above-mentioned reaction system；
(3) above-mentioned reaction drive body is poured into closed reactor, 120 DEG C of hydro-thermal reaction 72h；
(4) room temperature is down to the rate of 5 DEG C/h, obtains faint yellow bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain mesh
Product is marked, weighing, yield: 71%(is calculated based on CuI)；
(5) Cu-MOF crystallographic parameter is detailed in following table:
Embodiment 2
The preparation of Cu-MOF catalyst:
(1) CuI (0.019 gram, 0.1mmol) is added in 25mL polytetrafluoro reaction kettle, 3mL acetonitrile is added, room temperature is protected from light magnetic
After power stirs 30min；
(2) by N, N, N-tris (3-pyridinyl) -1,3,5-benzenetricarboxamide(TPB) ligand (0.028
Gram, 0.05mmol) stirring and dissolving in 4mL acetonitrile and is added dropwise in above-mentioned reaction system；
(3) above-mentioned reaction drive body is poured into closed reactor, 100 DEG C of hydro-thermal reaction 80h；
(4) room temperature is down to the rate of 5 DEG C/h, obtains faint yellow bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain mesh
Product is marked, weighing, yield: 75%(is calculated based on CuI).
Embodiment 3
The preparation of Cu-MOF catalyst:
(1) CuI (0.019 gram, 0.1mmol) is added in 25mL polytetrafluoro reaction kettle, 3mL acetonitrile is added, room temperature is protected from light magnetic
After power stirs 50min；
(2) by N, N, N-tris (3-pyridinyl) -1,3,5-benzenetricarboxamide(TPB) ligand (0.034
Gram, 0.06mmol) stirring and dissolving in 4mL acetonitrile and is added dropwise in above-mentioned reaction system；
(3) above-mentioned reaction drive body is poured into closed reactor, 110 DEG C of hydro-thermal reaction 60h；
(4) room temperature is down to the rate of 5 DEG C/h, obtains faint yellow bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain mesh
Product is marked, weighing, yield: 76%(is calculated based on CuI).
Embodiment 4
Cu-MOF catalyst cascade catalysis benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl and phenylacetylene prepared by embodiment 1:
(1) it is successively weighed into round-bottomed flask benzyl azide (0.113 gram, 1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram,
2mmol), phenylacetylene (0.099 gram, 1.3mmol) and K2CO3Magneton and solvent 1, bis- chloroethene of 2- is added in (0.276 gram, 2mmol)
Alkane (DCE, 5mL)；
(2) it is added Cu-MOF(0.072 grams to (1) reaction system again, 0.05mmol) it is used as catalyst；
(3) then reaction system (2) is placed in and reacts 8h at room temperature；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 95% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) δ: 8.15-8.21 (m, 2H), 7.32-7.48 (m, 10H), 6.90-6.92 (m, 2H), 5.67 (s,
2H), 3.86 (s, 3H), as shown in Figure 4.
Embodiment 5
Cu-MOF catalyst cascade catalysis benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl and 1- acetenyl -4- prepared by embodiment 1
Fluorobenzene:
(1) it is successively weighed into round-bottomed flask benzyl azide (0.113 gram, 1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram,
2mmol), 1- acetenyl -4- fluorobenzene (0.156 gram, 1.3mmol) and K2CO3Magneton and solvent 1 is added in (0.276 gram, 2mmol),
2- dichloroethanes (DCE, 5mL)；
(2) it is added Cu-MOF(0.072 grams to (1) reaction system again, 0.05mmol) it is used as catalyst；
(3) then reaction system (2) is placed in and reacts 8h at room temperature；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 95% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) δ: 8.15-8.22 (m, 2H), 7.32-7.51 (m, 9H), 6.90-6.92 (m, 2H), 5.66 (s,
2H), 3.86 (s, 3H), as shown in Figure 5.
Embodiment 6
Cu-MOF catalyst cascade catalysis benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl and 4- acetenyl-first prepared by embodiment 1
Benzene:
(1) it is successively weighed into round-bottomed flask benzyl azide (0.113 gram, 1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram,
2mmol), 4- acetenyl-toluene (0.151 gram, 1.3mmol) and K2CO3Magneton and solvent 1,2- is added in (0.276 gram, 2mmol)
Dichloroethanes (DCE, 5mL)；
(2) it is added Cu-MOF(0.072 grams to (1) reaction system again, 0.05mmol) it is used as catalyst；
(3) then reaction system (2) is placed in and reacts 9h at room temperature；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 94% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) δ: 8.05-8.09 (m, 2H), 7.30-7.48 (m, 9H), 6.85-6.94 (m, 2H), 5.65 (s,
2H), 3.86 (s, 3H), 2.38 (s, 3H), as shown in Figure 6.
Embodiment 7
Cu-MOF catalyst cascade catalysis benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl and 4- acetylenylbenzene prepared by embodiment 1
Nitrile:
(1) it is successively weighed into round-bottomed flask benzyl azide (0.113 gram, 1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram,
2mmol), 4- acetenyl cyanophenyl (0.165 gram, 1.3mmol) and K2CO3Magneton and solvent 1,2- is added in (0.276 gram, 2mmol)
Dichloroethanes (DCE, 5mL)；
(2) it is added Cu-MOF(0.072 grams to (1) reaction system again, 0.05mmol) it is used as catalyst；
(3) then reaction system (2) is placed in and reacts 10h at room temperature；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 93% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) δ: 8.26-8.33 (m, 2H), 7.68-7.74 (m, 9H), 7.33-7.46 (m, 7H), 6.93-6.97
(m, 2H), 5.67 (s, 2H), 3.87 (s, 3H), as shown in Figure 7.
Embodiment 8
Cu-MOF catalyst cascade catalysis benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl and 4- acetenyl connection prepared by embodiment 1
Benzene:
(1) it is successively weighed into round-bottomed flask benzyl azide (0.113 gram, 1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram,
2mmol), 4- acetenyl biphenyl (0.231 gram, 1.3mmol) and K2CO3Magneton and solvent 1,2- is added in (0.276 gram, 2mmol)
Dichloroethanes (DCE, 5mL)；
(2) it is added Cu-MOF(0.072 grams to (1) reaction system again, 0.05mmol) it is used as catalyst；
(3) then reaction system (2) is placed in and reacts 10h at room temperature；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 93% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) δ: 8.27-8.31 (m, 2H), 7.65-7.73 (m, 4H), 7.34-7.50 (m, 10H), 6.94-6.98
(m, 2H), 5.68 (s, 2H), 3.89 (s, 3H), as shown in Figure 8.
Embodiment 9
Recycle catalyst circulation catalyzed three-component series connection cycloaddition reaction:
(1) by the Cu-MOF filtered to isolate in embodiment 2 be used as again catalyst be added to containing benzyl azide (0.113 gram,
1mmol), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl (0.422 gram, 2mmol), phenylacetylene (0.099 gram, 1.3mmol) and K2CO3(0.276
Gram, 2mmol) 1,2- dichloroethanes (DCE, 5mL) solution in；
(2) then reaction system (1) is placed in and reacts 10h at room temperature；
(3) Cu-MOF then filtered to isolate continues to repeat same amount of experiment in embodiment 2 as catalyst；
(4) catalyst recycles ten times according to the above method, and specific method is same as above, as shown in Figure 9.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method based on copper complex heterogeneous catalysis material, it is characterised in that steps are as follows:
(a) cuprous iodide is dissolved in acetonitrile, stirring at normal temperature 30-50min obtains mixed solution；
(b) by the mixed solution of the acetonitrile solution dropwise of TPB ligand to step (a), stirring and dissolving；
(c) step (b) reaction solution is placed in closed reactor, 100-120 DEG C of hydro-thermal reaction 60-80h；
(d) after reacting, room temperature is down to the rate of 5 DEG C/h, yellowish crystal is obtained, is successively washed with distilled water and acetonitrile, it is dry,
Obtain target product copper complex.
2. the preparation method according to claim 1 based on copper complex heterogeneous catalysis material, it is characterised in that: described
The molar ratio of cuprous iodide and step (b) TPB ligand is 1:(0.3-0.6 in step (a)).
3. application of the copper complex of any of claims 1 or 2 in synthesis 5- alkynyl -1,2,3- triazole derivatives.
4. application of the copper complex according to claim 3 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is that steps are as follows:
(1) container is placed in using benzyl azide, the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl, fragrant alkynes, Anhydrous potassium carbonate as reaction substrate
In；
(2) catalyst copper complex is added into the reaction solution of step (1), reaction obtains 5- alkynyl -1,2, tri- nitrogen of 3- at room temperature
Zole derivatives.
5. application of the copper complex according to claim 4 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is: benzyl azide in the step (1), the bromo- 4- methyl phenyl ethers anisole of 1- alkynyl, fragrant alkynes, Anhydrous potassium carbonate molar ratio be
1:(1-1.5): (1.3-2): (2-4).
6. application of the copper complex according to claim 4 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is: the structural formula of the fragrance alkynes is, wherein R is H, F, Me, NC, Ph.
7. application of the copper complex according to claim 4 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is: the structural formula of the 5- alkynyl -1,2,3- triazole derivatives is, wherein R be H, F, Me,
NC、Ph。
8. application of the copper complex according to claim 4 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is: the molar ratio of catalyst and benzyl azide in step (1) is 0.05:1 in the step (2).
9. application of the copper complex according to claim 4 in synthesis 5- alkynyl -1,2,3- triazole derivatives, special
Sign is: the reaction time is 8-10h in the step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811085640.1A CN109134881B (en) | 2018-09-18 | 2018-09-18 | Preparation method and application of copper complex-based heterogeneous catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811085640.1A CN109134881B (en) | 2018-09-18 | 2018-09-18 | Preparation method and application of copper complex-based heterogeneous catalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134881A true CN109134881A (en) | 2019-01-04 |
| CN109134881B CN109134881B (en) | 2021-01-26 |
Family
ID=64814709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811085640.1A Active CN109134881B (en) | 2018-09-18 | 2018-09-18 | Preparation method and application of copper complex-based heterogeneous catalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134881B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905825A (en) * | 2020-08-19 | 2020-11-10 | 中原工学院 | Zinc coordination polymer catalytic material and preparation method and application thereof |
| CN113750971A (en) * | 2021-09-27 | 2021-12-07 | 中原工学院 | Adsorbing material based on zinc complex and preparation method and application thereof |
| CN114940763A (en) * | 2022-05-25 | 2022-08-26 | 中原工学院 | Metal organic framework material with reversible structure conversion, and preparation method and application thereof |
| CN115532318A (en) * | 2022-10-20 | 2022-12-30 | 江南大学 | MOF-loaded metal catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671673A (en) * | 2002-05-30 | 2005-09-21 | 斯克里普斯研究学院 | Copper-catalysed ligation of azides and acetylenes |
| US20130310569A1 (en) * | 2012-05-21 | 2013-11-21 | Hunaid Nulwala | Triazolide based ionic liquids |
| CN104592281A (en) * | 2014-12-19 | 2015-05-06 | 河南师范大学 | Bifunctional 4-TMS-5-I-1,2,3-triazole compound as well as preparation method and application thereof |
-
2018
- 2018-09-18 CN CN201811085640.1A patent/CN109134881B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671673A (en) * | 2002-05-30 | 2005-09-21 | 斯克里普斯研究学院 | Copper-catalysed ligation of azides and acetylenes |
| US20130310569A1 (en) * | 2012-05-21 | 2013-11-21 | Hunaid Nulwala | Triazolide based ionic liquids |
| CN104592281A (en) * | 2014-12-19 | 2015-05-06 | 河南师范大学 | Bifunctional 4-TMS-5-I-1,2,3-triazole compound as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| WEIGUO WANG ET AL: ""Copper(I)-Catalyzed Three-Component Click/Alkynylation: One-Pot Synthesis of 5-Alkynyl-1,2,3-triazoles"", 《ORG. LETT.》 * |
| 王晓璐: ""三角架氮配体/柔性羧酸配体构筑的配合物的结构及催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905825A (en) * | 2020-08-19 | 2020-11-10 | 中原工学院 | Zinc coordination polymer catalytic material and preparation method and application thereof |
| CN111905825B (en) * | 2020-08-19 | 2023-01-24 | 中原工学院 | Zinc coordination polymer catalytic material and preparation method and application thereof |
| CN113750971A (en) * | 2021-09-27 | 2021-12-07 | 中原工学院 | Adsorbing material based on zinc complex and preparation method and application thereof |
| CN113750971B (en) * | 2021-09-27 | 2023-07-21 | 中原工学院 | Adsorption material based on zinc complex and preparation method and application thereof |
| CN114940763A (en) * | 2022-05-25 | 2022-08-26 | 中原工学院 | Metal organic framework material with reversible structure conversion, and preparation method and application thereof |
| CN115532318A (en) * | 2022-10-20 | 2022-12-30 | 江南大学 | MOF-loaded metal catalyst and preparation method and application thereof |
| CN115532318B (en) * | 2022-10-20 | 2023-07-21 | 江南大学 | MOF-supported metal catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134881B (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109134881A (en) | A kind of preparation method and application based on copper complex heterogeneous catalysis material | |
| CN102190797B (en) | Quick synthesizing method of triazinyl covalent bond organic framework material with nano pores and application thereof | |
| CN108794756A (en) | A kind of preparation method and applications of the covalent organic frame material of nickel ion modification | |
| CN102633821B (en) | copper complex built by pyrimidine carboxylic acid base ligand, preparation method and use of copper complex | |
| CN108772102A (en) | Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester | |
| CN114195827B (en) | Carboxyl substituted ruthenium complex and preparation method and application thereof | |
| CN109369689B (en) | Copper metal organic framework (Cu-MOF) catalytic material, preparation method and application | |
| CN103949288B (en) | Molecular sieve supported Cu-Cp Schiff base complex, and preparation method and application thereof | |
| CN112592361B (en) | Fluoroboropyrrole functionalized metal organic framework material and preparation method and application thereof | |
| CN105503811A (en) | Preparation method of ethylene carbonate | |
| CN108892783B (en) | Visible light driven hydrogen production metal-organic framework material based on eosin and preparation method thereof | |
| CN107987015B (en) | A kind of asymmetric double pyridyl group olefin(e) compounds and its preparation method and application | |
| CN104437453A (en) | Carbon aerogel catalyst, as well as preparation method and application thereof | |
| Li et al. | A LADH-like Zn-MOF as an efficient bifunctional catalyst for cyanosilylation of aldehydes and photocatalytic oxidative carbon–carbon coupling reaction | |
| CN108722488B (en) | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof | |
| CN109675635A (en) | Natural polymer catalyst and preparation method thereof suitable for 2,3,6- oxidation of trimethylphenol | |
| CN114940763B (en) | Metal organic framework material with reversible structure conversion, and preparation method and application thereof | |
| CN107199051A (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof | |
| CN103977839B (en) | A kind of ionic organic metal tungstates epoxidation catalyst and preparation method thereof | |
| CN110586141A (en) | Preparation method of Ag-Bi solid solution composite photocatalyst for treating oil field waste liquid | |
| CN106964378B (en) | A kind of preparation method of fluorinated graphene composite visible light response catalyst | |
| CN112778153B (en) | Amido bridged hexacarboxylic acid ligand and metal organic framework material as well as preparation method and application thereof | |
| CN106540750B (en) | With visible light-responded small numerator modified catalysis material and preparation method | |
| CN111909221B (en) | Metal-organic framework material for visible light catalysis styrene bifunctional reaction, and preparation method and application thereof | |
| CN116554232A (en) | Trinuclear zirconium-based molecular cage, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |