CN114773222A - Synthetic method of azo micromolecules for zinc oxide nanoparticle stable ligand - Google Patents
Synthetic method of azo micromolecules for zinc oxide nanoparticle stable ligand Download PDFInfo
- Publication number
- CN114773222A CN114773222A CN202210537276.8A CN202210537276A CN114773222A CN 114773222 A CN114773222 A CN 114773222A CN 202210537276 A CN202210537276 A CN 202210537276A CN 114773222 A CN114773222 A CN 114773222A
- Authority
- CN
- China
- Prior art keywords
- azo
- water
- solution
- organic
- zinc oxide
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 21
- OAZFTIPKNPTDIO-UHFFFAOYSA-N 2-(6-bromohexyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCCCCBr)C(=O)C2=C1 OAZFTIPKNPTDIO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004440 column chromatography Methods 0.000 claims abstract description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000012074 organic phase Substances 0.000 claims description 34
- 229960001701 chloroform Drugs 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- BEYOBVMPDRKTNR-BUHFOSPRSA-N 4-Hydroxyazobenzene Chemical compound C1=CC(O)=CC=C1\N=N\C1=CC=CC=C1 BEYOBVMPDRKTNR-BUHFOSPRSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000284 extract Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- -1 aryl hydrazine Chemical compound 0.000 description 5
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001414 amino alcohols Chemical group 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009450 smart packaging Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing azo micromolecules for a zinc oxide nanoparticle stable ligand. Synthesizing a target molecule AZO-NH by adopting a two-step method2In the first step, 4-phenylazoylphenol and N- (6-bromohexyl) phthalimide are used as raw materials to synthesize a white intermediate, and in the second step, hydrazine hydrate and other reagents are added into the intermediate obtained in the first step, and the white intermediate is subjected to a series of steps such as extraction, drying, column chromatography and the likeFinally obtaining AZO-NH2. Reagents used in the experimental process are all nontoxic reagents, so that the safety of the experimental process can be ensured.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to a synthesis method of azo micromolecules for zinc oxide nano particle stable ligands.
Background
Azobenzene molecules are typical photoisomerization molecules, the structures of azobenzene molecules can be changed by light irradiation with different wavelengths, and azobenzene is applied to many fields such as dyes, medicines, liquid crystal materials and intelligent packaging. The synthesis methods of azobenzene and its derivatives are many, and mainly include diazo coupling method, nitro reduction method, aryl hydrazine oxidation method, arylamine oxidation method, and the like. However, the synthesis of the amino alcohol substituted azobenzene is only reported, and the synthesis steps are shown as follows, and toxic or easily explosive compounds (such as ammonia gas, sodium azide and the like) or strong reducing agents (lithium aluminum hydride and the like) are commonly used in the synthesis method, so that great potential safety hazards exist.
The invention adopts a two-step method to synthesize a target molecule AZO-NH2The structural formula of the intermediate synthesized in the first step is shown as the following formula 1, and the target molecule AZO-NH synthesized in the second step2The structural formula of (A) is shown in the following formula 2. The synthesis method avoids using toxic or explosive chemical reagents and is safe.
Based on the previous work that alkylamine with different alkyl chains can be used as a stable ligand to prepare zinc oxide nanoparticles, the AZO-NH with the same long alkyl chain is synthesized in the invention2Can be used as a stable ligand to prepare the zinc oxide nano particles.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for synthesizing AZO micromolecules for zinc oxide nanoparticle stable ligands, which adopts a two-step method to synthesize a target molecule AZO-NH2In the first step, 4-phenylazoylphenol and N- (6-bromohexyl) phthalimide are used as raw materials to synthesize a white intermediate, and in the second step, hydrazine hydrate and other reagents are added into the intermediate obtained in the first step, and the AZO-NH is finally obtained through a series of steps such as extraction, drying, column chromatography and the like2. Has been subjected to experimentsThe reagents used in the process are all nontoxic reagents, and the safety of the experimental process can be ensured.
The invention is realized by the following technical scheme:
the invention discloses a synthetic method of azo micromolecules for a nanoparticle stable ligand, which comprises the following steps:
1) adding 4-phenylazo phenol, potassium carbonate and N, N-dimethylformamide into N- (6-bromohexyl) phthalimide under the protection of inert gas, heating the system to more than 100 ℃ under stirring, placing the obtained suspension into a separating funnel after the reaction is finished, adding an organic solvent and a water solution into the suspension, extracting the water phase with the organic solvent, combining the organic phases, respectively washing the organic phases with alkali liquor and water, drying, filtering and concentrating under reduced pressure to obtain an intermediate product, namely a white solid;
2) dissolving the intermediate product white solid obtained in the step 1) in an alcohol solution, heating and refluxing the system, adding hydrazine hydrate, enabling the mixture to be colorless firstly, then forming a white precipitate, continuously stirring and refluxing, spin-drying, adding an organic solvent, water and an alkali liquor, separating an organic phase, extracting a water phase by using the organic solvent, combining the organic phases, then respectively washing the organic phases by using the alkali liquor and water, drying, filtering, concentrating under reduced pressure, and purifying by column chromatography to obtain a light yellow product AZO-NH2；
3) Using diethyl zinc as a precursor, and obtaining AZO-NH by the step 2) with two equivalents2Preparing the zinc oxide nano particles for the ligand.
As a further improvement, in step 1) of the present invention, the structural formula of the synthesized intermediate product is shown in formula 1:
as a further improvement, in the step 2) of the invention, the synthesized AZO-NH2The structural formula is shown as formula 2:
as a further improvement, in the step 1) of the invention, the molar ratio of the compound 4-phenylazoylphenol to the compound N- (6-bromohexyl) phthalimide is 1: 1 to 1.5: 1.
As a further improvement, in step 1) of the present invention, the molar ratio of the compound N- (6-bromohexyl) phthalimide to the potassium carbonate is 1: 2.
as a further improvement, in step 1) of the synthesis according to the present invention, the reaction is carried out at 120 ℃ with stirring, and the resulting suspension is added with ethyl acetate, chloroform and water (to facilitate separation) during liquid separation, and the organic phases are combined and washed with a saturated sodium hydroxide solution.
As a further improvement, in step 2) of the present invention, a lye is slowly added dropwise before the separation of the organic phase so that the pH of the solution is greater than 10.
As a further improvement, in the step 2) of the invention, the eluent used for column chromatography purification is a mixed solvent of dichloromethane and methanol or trichloromethane and methanol in a ratio of 83:155:1.55, and ammonia is added to balance the system.
As a further improvement, in the step 2) of the invention, the reaction is carried out in an ethanol solution and heated to 90 ℃ for refluxing; slowly dropwise adding hydrazine hydrate into the reaction system.
The invention has the following beneficial effects:
the preparation method provided by the invention can be used for synthesizing the amino alcohol substituted azobenzene compound through two-step continuous reaction, and the reaction intermediate 1 does not need column chromatography separation, so that the yield can be improved. The raw materials used in the reaction do not contain toxic and harmful reagents such as ammonia gas, sodium azide and the like, so that the experimental risk is effectively reduced, and the environmental pollution is reduced.
When the intermediate 1 is synthesized, ethyl acetate, chloroform and water are added into the obtained suspension during liquid separation, so that layering is facilitated, the problems of difficult separation and the like caused by solution emulsification are solved, and the product yield is improved.
The method is used for preparing the compound AZO-NH2In the process, the alkali liquor is used for regulating the system before the separation of the organic phaseFinal pH above 10 can reduce product loss. A small amount of ammonia water is added during column chromatography purification, so that tailing can be prevented, and a better separation effect is achieved.
The long alkyl chain compound AZO-NH synthesized by the preparation method provided by the invention2Can be used as a stable ligand of the zinc oxide nanoparticles to efficiently prepare stable nanoparticles, and the absorption spectrum of the prepared zinc oxide nanoparticles is gradually enhanced under the irradiation of blue light, so that the zinc oxide nanoparticles have good optical activity.
The preparation method provided by the invention has relatively mild conditions, does not need to add strong reducing or acyl chlorination reagents such as lithium aluminum hydride, thionyl chloride and the like, can generate the target product only by heating, and solves the problems of low yield, large heat release of reaction, cost increase caused by three-waste treatment and the like.
Drawings
FIG. 1 is a NMR chart of an intermediate obtained in example 1;
FIG. 2 shows AZO-NH obtained in example 12The polarization microscope photograph of (1);
FIG. 3 is a transmission electron micrograph of the zinc oxide nanoparticles obtained in example 1, magnified 50000 times;
FIG. 4 is a transmission electron micrograph of the zinc oxide nanoparticles obtained in example 1 with a magnification of 200000 times;
FIG. 5 shows the two equivalents of AZO-NH obtained in example 12A polarizing microscope photo of the zinc oxide nanoparticles under ligand stability;
FIG. 6 shows AZO-NH obtained in example 12Ultraviolet visible absorption spectrogram of molecular chloroform solution under 365nm ultraviolet irradiation;
FIG. 7 shows AZO-NH obtained in example 12Ultraviolet-visible absorption spectrum of molecular chloroform solution under 436nm blue light irradiation.
Detailed Description
The invention discloses a synthetic method of azo micromolecules for a nanoparticle stable ligand, which comprises the following steps:
(1) 4-N-phenylbenzamide, potassium carbonate and N, N-dimethylformamide were added under an argon atmosphere to a pre-dried round-bottom flask, followed by N- (6-bromohexyl) phthalimide, and the mixture was stirred at 120 ℃ until the reaction was complete. The resulting suspension was placed in a separatory funnel and some ethyl acetate, chloroform, and water were added. The organic phase is used as raw material, ethyl acetate is used as extractant, and the residue in the aqueous solution is extracted. The organic phase was collected and washed with saturated sodium hydroxide solution. Drying the obtained solution with anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure to obtain intermediate white solid as shown in formula 1
(2) Placing the ethanol suspension of the product obtained in step (1) in a pre-dried two-necked round-bottom flask. The mixture was heated to 90 ℃ and the hydrazine hydrate solution was added dropwise over 10 minutes. The mixture was found to turn colorless first and then a white precipitate was formed. The mixture system was stirred under reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water, chloroform, and methanol, separated in a separatory funnel and some precipitate was observed to be insoluble in the organic phase, then 2ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform, the organic extracts were combined and washed with saturated sodium bicarbonate solution, then the organic extract was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, column chromatography purification is carried out by using chloroform, methanol and ammonia water (83:155:1.55) eluent to obtain a light yellow product AZO-NH2This is shown in the following formula 2.
The technical solution of the present invention is further illustrated by the following specific examples:
example 1:
(1) 4-N-phenylbenzamide (1.88g,9.47mmol), potassium carbonate (2.35g,17.0mmol) and N, N-dimethylformamide (50ml) were added under an argon atmosphere to a pre-dried round bottom flask, followed by N- (6-bromohexyl) phthalimide (2.63g,8.5mmol) and the mixture stirred at 120 ℃ until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL ethyl acetate, chloroform, and water (volume ratio 3: 2: 5) were added. And extracting the residue in the water solution by using the organic phase as a raw material and ethyl acetate as an extracting agent. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (3.25g, yield 90%), characterized by nuclear magnetic hydrogen spectroscopy (FIG. 1),1H NMR(500MHz,DMSO-d6)δ7.91-7.84(m,6H),7.71-7.62(m,2H),7.58-7.37(m,2H),6.88-7.05(m,2H),4.03(t,J＝6.5Hz,2H),3.71(t,J＝6.5Hz,2H),1.90-1.72(m,4H),1.38-1.65(m,4H)。
(2) placing the ethanol suspension of the product obtained in step (1) in a pre-dried two-necked round-bottom flask. The mixture was warmed to 90 ℃ and hydrazine hydrate (740. mu.l) was added dropwise over 10 minutes. The mixture was found to turn colorless first and then a white precipitate was formed. The mixture system was stirred at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water (200ml), chloroform (200ml), and methanol (5ml), separated in a separatory funnel and some precipitate was observed to be insoluble in the organic phase, so 2ml of sodium hydroxide solution was added dropwise to a pH above 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3 × 100ml), the organic extracts were combined and washed with saturated sodium bicarbonate solution, then the organic extract was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, column chromatography purification is carried out by using chloroform, methanol and ammonia water (83:155:1.55) eluent to obtain a light yellow product AZO-NH2(1.89g, yield 75%), characterization by nuclear magnetic resonance1H NMR(500MHz,CDCl3)8.42-8.37(m,2H),8.21-8.28(m,2H),7.94-7.78(m,4H),4.05(t, J ═ 6.4Hz,2H, CH2),2.72(t, J ═ 7.2Hz,2H, CH2),2.21(t, J ═ 6.4Hz,2H, CH2),1.65-1.56(m,2H),1.31-1.22(m, 4H). Compound observation by polarizing microscopeAZO-NH2Form (FIG. 2). The compound was dissolved in chloroform and the UV-Vis absorption spectra were measured as a function of time under 365nm UV irradiation (FIG. 6) and 436nm blue light irradiation (FIG. 7), respectively.
(3) Takes diethyl zinc as a precursor and has two equivalents of AZO-NH2Can prepare zinc oxide nano particles for ligand. The transmission electron micrographs of the compound AZO-NH were observed with a polarizing microscope in FIGS. 3 (50000 times magnification) and 4 (200000 times magnification)2Form (FIG. 5).
Example 2:
(1) 4-N-phenylbenzamide (2.15g,10.85mmol), potassium carbonate (2.70g,19.5mmol) and N, N-dimethylformamide (50ml) were added under an argon atmosphere to a pre-dried round bottom flask, followed by N- (6-bromohexyl) phthalimide (2.70g,9.8mmol) and the mixture stirred at 120 ℃ until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL ethyl acetate, chloroform and water were added. The organic phase is used as raw material, ethyl acetate is used as extractant, and the residue in the aqueous solution is extracted. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a white solid (3.45g, yield 83%).
(2) Placing the ethanol suspension of the product obtained in step (1) in a pre-dried two-necked round-bottom flask. The mixture was heated to 90 ℃ and hydrazine hydrate (850. mu.l) was added dropwise over 10 minutes. The mixture was found to turn colorless first and then a white precipitate was formed. The mixture was stirred under reflux at a predetermined temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water (200ml), chloroform (200ml), and methanol (5ml), separated in a separatory funnel and some precipitate was observed to be insoluble in the organic phase, so 3ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3 × 100ml), the organic extracts were collected and washed with saturated sodium bicarbonate solution, then the organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, column chromatography purification is carried out by using chloroform, methanol and ammonia water (83:155:1.55) as eluent to obtain light yellow productProduct AZO-NH2(1.87g, yield 78%).
(3) Takes diethyl zinc as a precursor and has two equivalents of AZO-NH2Can prepare zinc oxide nano particles for ligand.
Example 3:
(1) 4-N-Phenylbenzamide (1.43g, 7.21mmol), potassium carbonate (1.80g, 13.0mmol) and N, N-dimethylformamide (50ml) were added under an argon atmosphere to a pre-dried round bottom flask, followed by N- (6-bromohexyl) phthalimide (2.02g,6.5mmol) and the mixture stirred at 120 ℃ until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL ethyl acetate, chloroform and water were added. The organic phase is used as raw material, ethyl acetate is used as extractant, and the residue in the aqueous solution is extracted. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a white solid (2.60g, yield 94%).
(2) Placing the ethanol suspension of the product obtained in step (1) in a pre-dried two-necked round-bottom flask. The mixture was heated to 90 ℃ and hydrazine hydrate solution (570. mu.l) was added dropwise over 10 minutes. The mixture was found to turn colorless first and then a white precipitate was formed. The mixture was stirred under reflux at a predetermined temperature until the reaction was complete. Volatile components were removed under vacuum, and the residue was dissolved in a mixed solvent of water (200ml), chloroform (200ml), and methanol (5ml), separated in a separatory funnel, and some precipitate was observed to be insoluble in the organic phase, so 2ml of sodium hydroxide solution was added dropwise to a pH of more than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (100ml), the organic extracts were collected and washed with saturated sodium bicarbonate solution, and then the organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, column chromatography purification is carried out by eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a light yellow product AZO-NH2(1.81g, yield 80%).
(3) Takes diethyl zinc as a precursor and has two equivalents of AZO-NH2Can prepare zinc oxide nano particles for ligand.
Example 4:
(1) 4-N-phenylbenzamide (2.69g, 13.6mmol), potassium carbonate (3.40g,24.6mmol) and N, N-dimethylformamide (50ml) were added under an argon atmosphere to a pre-dried round bottom flask, followed by N- (6-bromohexyl) phthalimide (3.82g, 12.3mmol) and the mixture stirred at 120 ℃ until the reaction was complete. The resulting suspension was placed in a separatory funnel and 150mL of ethyl acetate, chloroform, and water were added. The organic phase is used as raw material, ethyl acetate is used as extractant, and the residue in the aqueous solution is extracted. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (4.88g, yield 93%).
(2) Placing the ethanol suspension of the product obtained in step (1) in a pre-dried two-necked round-bottom flask. The mixture was warmed to 90 ℃ and hydrazine hydrate solution (1070 μ l) was added dropwise over 10 minutes. The mixture was found to turn colorless first and then a white precipitate was formed. The mixture was stirred under reflux at a predetermined temperature until the reaction was complete. Volatile components were removed under vacuum, and the residue was dissolved in a mixed solvent of water (200ml), chloroform (200ml), and methanol (5ml), separated in a separatory funnel, and some precipitate was observed to be insoluble in the organic phase, so 6ml of sodium hydroxide solution was added dropwise to a pH of more than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3 × 100ml), the organic extracts were collected and washed with saturated sodium bicarbonate solution, then the organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, column chromatography purification is carried out by using chloroform, methanol and ammonia water (83:155:1.55) eluent to obtain a light yellow product AZO-NH2(2.58g, yield 76%).
(3) Takes diethyl zinc as a precursor and has two equivalents of AZO-NH2The zinc oxide nano particles can be prepared as the ligand.
While only a few specific embodiments of the present invention have been shown and described, it will be obvious that the invention is not limited thereto, but may be embodied in many different forms and that all changes and modifications that can be derived from the disclosure set forth herein by one of ordinary skill in the art are deemed to be within the scope of the present invention.
Claims (8)
1. A synthetic method of azo micromolecules for stabilizing ligands of nanoparticles is characterized by comprising the following steps:
1) adding 4-phenylazo phenol, potassium carbonate and N, N-dimethylformamide into N- (6-bromohexyl) phthalimide under the protection of inert gas, heating the system under stirring, placing the obtained suspension into a separating funnel after the reaction is finished, adding an organic solvent and a water solution, extracting the water phase with the organic solvent, combining the organic phases, respectively washing the organic phases with alkali liquor and water, drying, filtering, and concentrating under reduced pressure to obtain an intermediate product, namely a white solid;
2) dissolving the intermediate product white solid obtained in the step 1) in an alcohol solution, heating and refluxing the system, adding hydrazine hydrate, enabling the mixture to be colorless firstly, then forming a white precipitate, continuously stirring and refluxing, spin-drying, adding an organic solvent, water and an alkali liquor, separating an organic phase, extracting a water phase by using the organic solvent, combining the organic phases, then respectively washing the organic phases by using the alkali liquor and water, drying, filtering, concentrating under reduced pressure, and purifying by column chromatography to obtain a light yellow product AZO-NH2；
3) Using diethyl zinc as a precursor, obtaining AZO-NH in the step 2) with two equivalents2Preparing the zinc oxide nano particles for the ligand.
2. The method of claim 1, wherein in step 1), the intermediate product synthesized has a formula shown in formula 1:
3. the method according to claim 1, wherein in step 2), the AZO-NH is synthesized2The structural formula is shown as formula 2:
4. the process according to claim 1, 2 or 3, wherein in step 1), the molar ratio of the compound 4-phenylazoylphenol to the compound N- (6-bromohexyl) phthalimide is 1: 1 to 1.5: 1.
5. The method according to claim 1, wherein in step 1), the molar ratio of the compound N- (6-bromohexyl) phthalimide to the potassium carbonate is 1: 2.
6. the method according to claim 1, wherein in step 1), in the synthesis step 1), the reaction is carried out at 120 ℃ with stirring, the obtained suspension is subjected to liquid separation by adding ethyl acetate, chloroform and water (to facilitate separation), and the organic phases are combined and washed with a saturated sodium hydroxide solution.
7. A process according to claim 1 or 2 or 3 or 5 or 6, wherein in step 2) a base solution is slowly added dropwise to bring the pH of the solution to above 10 before the separation of the organic phase.
8. The preparation method according to claim 7, wherein in the step 2), the eluent used for column chromatography purification is a mixed solvent of dichloromethane and methanol or trichloromethane and methanol, and an ammonia water balance system is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537276.8A CN114773222B (en) | 2022-05-16 | 2022-05-16 | Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537276.8A CN114773222B (en) | 2022-05-16 | 2022-05-16 | Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114773222A true CN114773222A (en) | 2022-07-22 |
| CN114773222B CN114773222B (en) | 2024-04-09 |
Family
ID=82436078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210537276.8A Active CN114773222B (en) | 2022-05-16 | 2022-05-16 | Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773222B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013139A (en) * | 2007-07-09 | 2009-01-22 | Nara Institute Of Science & Technology | Azopeptide complex |
| CN105431379A (en) * | 2013-08-02 | 2016-03-23 | 国立研究开发法人产业技术综合研究所 | Dispersant-containing carbon material film containing light-responsive dispersant, and method for producing carbon material film using said dispersant-containing carbon material film |
| CN105586031A (en) * | 2015-11-11 | 2016-05-18 | 广西大学 | Azobenzene fluorescence sensor and preparation method and application thereof |
-
2022
- 2022-05-16 CN CN202210537276.8A patent/CN114773222B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013139A (en) * | 2007-07-09 | 2009-01-22 | Nara Institute Of Science & Technology | Azopeptide complex |
| CN105431379A (en) * | 2013-08-02 | 2016-03-23 | 国立研究开发法人产业技术综合研究所 | Dispersant-containing carbon material film containing light-responsive dispersant, and method for producing carbon material film using said dispersant-containing carbon material film |
| CN105586031A (en) * | 2015-11-11 | 2016-05-18 | 广西大学 | Azobenzene fluorescence sensor and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ，SHINKAI SEIJI ET AL.: "Photoresponsive crown ethers. 19. Photocontrol of reversible association-dissociation phenomena in tail(ammonium)-biting crown ethers", BULL. CHEM. SOC. JPN., vol. 60, no. 5, pages 1819 - 1824 * |
| SHINKAI SEIJI ET AL.: "Photoresponsive Crown Ethers. Part 14.t Photoregulated Crown-Metal Complexation by Competitive Intramolecular Tail(Ammonium)-biting", J. CHEM. SOC. PERKIN TRANS. II, no. 4, pages 511 - 518 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773222B (en) | 2024-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192108B (en) | Preparation method of hybrid supramolecular material with near-infrared light stimulus responsiveness based on pillararene host-guest action | |
| CN111548368B (en) | Copper nanocluster with high stability and near-infrared phosphorescence and preparation method thereof | |
| CN102807591A (en) | Double benzimidazole ligand based metal complex and preparation method and application thereof | |
| CN108129385B (en) | Composite quaternary ammonium salt nonlinear optical crystalline material and preparation method thereof | |
| CN110684202A (en) | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof | |
| Wang et al. | Different structures modulated mechanochromism and aggregation-induced emission in a series of Gold (I) complexes | |
| CN114044792A (en) | One-step synthesis method of 2-substituted metal iridium heterocarbulone complex | |
| CN113816910B (en) | Green synthesis of metal-free BCN photocatalytic benzoxazole compound | |
| CN112029107B (en) | Triazine ligand-based two-dimensional metal organic framework material and preparation method and application thereof | |
| CN110105379A (en) | A kind of Zn-MOFs complex preparation method with fluorescence identifying | |
| CN114773222A (en) | Synthetic method of azo micromolecules for zinc oxide nanoparticle stable ligand | |
| CN109675525B (en) | Preparation of metal supermolecule organogel and application of metal supermolecule organogel in adsorbing and separating methylene blue | |
| CN115161016B (en) | Sensor for detecting kaempferol and quercetin in tobacco leaves and preparation method thereof | |
| CN114957310A (en) | Trisilyl polycarboxylic organic silicon compound and synthesis method and application thereof | |
| CN113444117B (en) | Star-shaped compound of BODIPY bridged tetraperylene diimide derivative and preparation method thereof | |
| CN113845534B (en) | Preparation method and application of high-manganese acid radical luminescent crystal material for extremely sensitive aqueous phase detection | |
| CN109265484B (en) | Metal iridium-triazole crystal-graphene oxide ternary nonlinear optical material and preparation method thereof | |
| CN114874145A (en) | Water-soluble trityl free-based material and preparation method and application thereof | |
| CN109232616B (en) | (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof | |
| CN114773396B (en) | Terpyridine platinum (II) complex and preparation method and application thereof | |
| CN105384744B (en) | Four (trifluoro ethoxy) phthalocyanine europium complexes and its preparation method and application | |
| CN113896899B (en) | Supramolecular polymer material with aggregation-induced emission performance and stimulus responsiveness and preparation method thereof | |
| CN111499520B (en) | Nitrogen-containing tetradentate ligand, intermediate and preparation method thereof | |
| CN110066298B (en) | Platinum metal gel material and preparation method and application thereof | |
| CN115925683B (en) | Dendritic carbazole pyridine formaldehyde compound, preparation method and application |
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 |