CN105906670B - A kind of Fluorenone pyridine nickel nano-cluster and preparation method thereof - Google Patents
A kind of Fluorenone pyridine nickel nano-cluster and preparation method thereof Download PDFInfo
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- CN105906670B CN105906670B CN201610280894.3A CN201610280894A CN105906670B CN 105906670 B CN105906670 B CN 105906670B CN 201610280894 A CN201610280894 A CN 201610280894A CN 105906670 B CN105906670 B CN 105906670B
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- C07—ORGANIC CHEMISTRY
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- 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
- B01J31/22—Organic complexes
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/88—Growth and elimination reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- 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
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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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
- 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
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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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
- 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
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The invention discloses a kind of Fluorenone pyridine nickel nano-clusters and preparation method thereof, Fluorenone pyridine organic ligands solution is added dropwise in metal salt solution in the present invention, ultrasonic disperse after reaction, it centrifuges, washing, corresponding ligand metal nano-cluster is made in vacuum drying, and preparation process is simple, at low cost；By changing solvent, concentration, reaction time and the temperature of reactant realize the Effective Regulation to nano-cluster pattern.Fluorenone pyridine nickel nano-cluster prepared by the present invention can efficient catalytic C C cross-coupling reactions, yield is up to 70% or more.Therefore the Fluorenone pyridine nickel nano-cluster has wide application in catalytic field.
Description
Technical field
The invention belongs to metal organic nanocomposite fields, and in particular to intersect occasionally for being catalyzed carbon-to-carbon to one kind
Join the Fluorenone pyridine nickel nano-cluster and preparation method thereof of reaction.
Background technology
Carbon-carbon cross coupling reaction is one of most important means in organic synthesis, and synthesis biaryl chemical combination
One of object most efficient method is always the research hotspot in the fields such as catalytic chemistry, organic chemistry and materials chemistry.Traditional urges
Agent is mainly Pd (PPh3)4Etc. palladium metals organic catalyst, the catalytic activity of this kind of catalyst is high, and substrate range of choice is wide, but
It is easy to aromatic hydrocarbons occur easily to be formed in aryl exchange reaction, reaction process palladium black, building-up process are complicated, difficulty is big, it is expensive,
Phosphine ligands need effectively be catalyzed reaction in an inert gas atmosphere, pollute environment etc. many to air and moisture-sensitive
Deficiency, therefore, to find new and effective cheap catalyst, researchers' unremitting effort always.
In recent years, new and effective non-Phosphine ligands are developed or the catalyst system and catalyzing without ligand is more paid close attention to by people, and
Certain progress is obtained, a kind of palladium nanoparticle catalyst reported such as P é rez-Lorenzo
(J.Phys.Chem.Lett.2012,3,167) a kind of spiro fluorene pyridine palladium nano-particles and its preparation and disclosed in Zhao Xiuhua et al.
Method (CN103951611A, 2014.7.30 are disclosed), these catalyst activities are good, and preparation process is relatively easy, but still select
With expensive Metal Palladium, the relatively high and stable property of cost is not good enough；Cheap metallic nickel is selected to replace precious metal palladium in the present invention
It is prepared for a kind of nanocomposite, the atomic radius of nickel is smaller than palladium metal radius, and nucleophilie nucleus ability is strong, not to the electronegativity of substrate
Such as Pd sensitivities, there is universal application.
The selection of ligand plays a crucial role the activation of metal with stabilization.With it has been reported that or disclosed nickel urge
Change material and compares (J.Am.Chem.Soc.2006,128,5361；J.Am.Chem.Soc.2013,135,624；
CN104668577A, 2015.6.3 are disclosed；CN104628628A, 2015.5.20 are disclosed), the present invention in Fluorenone pyridine it is organic
Pyridine ring, phenyl ring and the five-membered ring for including in ligand form the conjugation big pi bond of delocalization, have specific HOMO highest occupied molecular orbital (HOMO)
With lowest unoccupied molecular orbital (LUMO) energy level, nitrogen-atoms is easy to be coordinated with nickel ion in pyridine ring, the conjugation delocalization electricity of organic ligand
Son generates specific effect to the valence electron d tracks of Ni (II), to change the catalytic activity of Ni (II)；In addition, Fluorenone pyridine is matched
There are C=O bonds on 9 in body, also will produce unique influence to the delocalization of ligand electronics, when it being made to be coordinated with nickel (II)
The external electronic shells structure of nickel ion is had an impact, thus forms the nanocomposite with unique physico-chemical property.
Invention content
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of cheap, preparation letter
The Fluorenone pyridine nickel nano-cluster and preparation method thereof of list and high catalytic efficiency.
Used technical solution is the present invention to solve above-mentioned technical problem：A kind of Fluorenone of efficient catalytic coupling reaction
The preparation method of pyridine nickel nano-cluster, includes the following steps：
(1) Fluorenone pyridine organic ligands are dissolved in be configured in solvent a concentration of 10~20mmol/L Fluorenone pyridine it is organic
Ligand solution is labeled as solution A；
(2) nickel salt is dissolved in the nickel salt aqueous solution that a concentration of 5~10mmol/L is configured in deionized water, it is molten labeled as B
Liquid；
(3) with vigorous stirring, (the object of Fluorenone pyridine organic ligands and nickel ion is slowly added dropwise into B solution in solution A
The ratio between amount of matter is 2~4:1) continue to be vigorously stirred after, being added dropwise, and 30~60min is reacted in 60~90 DEG C, reaction terminates
Afterwards by mixture ultrasonic disperse 30min, centrifuges, discard supernatant liquid, obtain sediment；
(4) gained sediment is washed with deionized water and ethyl alcohol respectively, ultrasonic disperse, centrifuges, it is molten discards upper layer
Lower sediment thing is then dried in vacuo to get the Fluorenone pyrrole by organic ligand of the liquid to remove free ion and not be coordinated
Pyridine nickel nano-cluster；
Preferably, the solvent is the one or any combination in propyl alcohol, isopropanol, ethyl alcohol；
Preferably, the nickel salt is one or more of nickel chloride, nickel acetate or nickel nitrate；
Preferably, entitled 2,7- bis- (4- pyridines) -9-Fluorenone of the Fluorenone pyridine organic ligands, molecular formula are
C23H14N2O。
Preferably, the Fluorenone pyridine nickel nano-cluster is as effective catalyst catalysis carbon-carbon cross coupling reaction.
The present invention also provides a kind of Fluorenone pyridine nickel nano-cluster, the Fluorenone pyridine nickel nano-cluster is according to above-mentioned Fluorenone pyrrole
The preparation method of pyridine nickel nano-cluster is prepared.
Compared with prior art, advantages of the present invention is as follows：
(1) electron delocalization of the Fluorenone pyridine organic ligands is strong, can be in two different directions coordinated with nickel ion,
Formed Fluorenone pyridine nickel nano-cluster, the nanocluster material performance stablize, can efficient catalytic coupling reaction, yield be up to 70% with
On.
(2) there are C=O bonds in the Fluorenone pyridine organic ligands, this also generates uniqueness to the delocalization of ligand electronics
Influence, when Fluorenone pyridine ligand and nickel ion are coordinated, delocalizedπelectron generates shadow to the valence shell electron level structure of nickel ion
It rings, to make the nickel nano-cluster to be formed that there is unique physico-chemical property.
(3) present invention selects cheap nickel salt, reduces catalyst cost；It is real and by controlling reaction time and temperature
Now to the regulation and control of Fluorenone pyridine nickel nano-cluster pattern, good catalytic performance is made it have.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of Fluorenone pyridine nickel nano-cluster of the present invention.
Specific implementation mode
Present invention is further described in detail with reference to embodiments.
Embodiment 1
With vigorous stirring, the aqueous isopropanol (10mmol/L, 15mL) of Fluorenone pyridine is slowly dropped to nickel nitrate water
Solution (5mmol/L, 15mL), continuing vigorous stirs and reacts 60min at 60 DEG C, after reaction by mixed system through ultrasound
Disperse 30min, centrifuges, discard upper liquid, obtain sediment；Gained sediment is washed with deionized water and ethyl alcohol respectively
Wash, ultrasonic disperse, centrifuge, the organic ligand for discarding upper solution to remove free ion and not be coordinated, then will under
Layer sediment vacuum drying is to get the Fluorenone pyridine nickel nano-cluster.The pattern of the nano-cluster described in scanning electron microscopic observation is such as schemed
Shown in 1.
Embodiment 2
With vigorous stirring, that the propanol solution (20mmol/L, 15mL) of Fluorenone pyridine is slowly dropped to nickel chloride is water-soluble
Liquid (5mmol/L, 15mL), continuing vigorous stir and react 30min at 90 DEG C, after reaction by mixed system through ultrasound point
30min is dissipated, is centrifuged, is discarded upper liquid, obtain sediment；Gained sediment is washed with deionized water and ethyl alcohol respectively,
Ultrasonic disperse, centrifuges, and the organic ligand for discarding upper solution to remove free ion and not be coordinated then sinks lower layer
Starch is dried in vacuo to get the Fluorenone pyridine nickel nano-cluster.The pattern of the nano-cluster described in scanning electron microscopic observation.
Embodiment 3
With vigorous stirring, that the ethanol solution (20mmol/L, 15mL) of Fluorenone pyridine is slowly dropped to nickel acetate is water-soluble
Liquid (10mmol/L, 15mL), continuing vigorous stirs and reacts 60min at 90 DEG C, after reaction by mixed system through ultrasound
Disperse 30min, centrifuges, discard upper liquid, obtain sediment；Gained sediment is washed with deionized water and ethyl alcohol respectively
Wash, ultrasonic disperse, centrifuge, the organic ligand for discarding upper solution to remove free ion and not be coordinated, then will under
Layer sediment vacuum drying is to get the Fluorenone pyridine nickel nano-cluster.The pattern of the nano-cluster described in scanning electron microscopic observation.
Embodiment 4
With vigorous stirring, that the ethanol solution (15mmol/L, 15mL) of Fluorenone pyridine is slowly dropped to nickel acetate is water-soluble
Liquid (6mmol/L, 15mL), continuing vigorous stir and react 50min at 80 DEG C, after reaction by mixed system through ultrasound point
30min is dissipated, is centrifuged, is discarded upper liquid, obtain sediment；Gained sediment is washed with deionized water and ethyl alcohol respectively,
Ultrasonic disperse, centrifuges, and the organic ligand for discarding upper solution to remove free ion and not be coordinated then sinks lower layer
Starch is dried in vacuo to get the Fluorenone pyridine nickel nano-cluster.The pattern of the nano-cluster described in scanning electron microscopic observation.
With embodiment 1, embodiment 2 for Fluorenone pyridine nickel nano-cluster prepared by embodiment 3 and embodiment 4, is catalyzed
C-C cross-coupling reactions：
Using Fluorenone pyridine nickel nano-cluster prepared by above-described embodiment 1 catalysis reaction, reaction condition are carried out as catalyst
For：By 1.0mmol 4- methoxybromobenzenes, 1.2mmol phenyl boric acids and 3.0mmol KOH, in H in air atmosphere2O/EtOH
(3mL/4mL) in the mixed solvent is reacted, and 8h, yield 75% are reacted at 90 DEG C.Reaction equation is as follows：
Using Fluorenone pyridine nickel nano-cluster prepared by above-described embodiment 2 catalysis reaction, reaction condition are carried out as catalyst
For：By 1.0mmol 4- iodobenzenes ether, 1.2mmol styrene and 3.0mmol K2CO3, in H in air atmosphere2O/EtOH
(3mL/4mL) in the mixed solvent is reacted, and 6h, yield 96% are reacted at 80 DEG C.Reaction equation is as follows：
Using Fluorenone pyridine nickel nano-cluster prepared by above-described embodiment 3 catalysis reaction, reaction condition are carried out as catalyst
For：By 1.0mmol 4- iodobenzenes ether, 1.2mmol styrene and 2.0mmol Na2CO3, in N, N- dimethyl in air atmosphere
Reaction, reacts 15h, yield 85% at 140 DEG C in formamide (DMF).Reaction equation is as follows：
Using Fluorenone pyridine nickel nano-cluster prepared by above-described embodiment 4 catalysis reaction, reaction condition are carried out as catalyst
For：By 1.0mmol iodobenzenes, 1.2mmol phenylacetylenes and 3.0mmol NaOH, in H in air atmosphere2O/EtOH(1mL/6mL)
In the mixed solvent is reacted, and 4h, yield 80% are reacted at 80 DEG C.Reaction equation is as follows：
Claims (2)
1. a kind of preparation method of Fluorenone pyridine nickel nano-cluster, it is characterised in that the preparation method comprises the following steps：
Fluorenone pyridine organic ligands are dissolved in be configured in solvent a concentration of 10~20mmol/L Fluorenone pyridine organic ligands it is molten
Liquid is labeled as solution A；
Nickel salt is dissolved in the nickel salt aqueous solution for being configured to a concentration of 5~10mmol/L in deionized water, is labeled as B solution；
With vigorous stirring, solution A is slowly added dropwise into B solution, the amount of the substance of Fluorenone pyridine organic ligands and nickel ion
The ratio between be 2~4:1, continue to be vigorously stirred after being added dropwise, and 30~60min is reacted in 60~90 DEG C, will mix after reaction
Object ultrasonic disperse 30min is closed, is centrifuged, is discarded supernatant liquid, obtain sediment；
Gained sediment is washed with deionized water and ethyl alcohol respectively, ultrasonic disperse, centrifuges, discard upper solution to remove
Lower sediment thing is then dried in vacuo to get the Fluorenone pyridine nickel nanometer by free ion and the organic ligand not being coordinated
Cluster；
The solvent is the one or any combination in propyl alcohol, isopropanol, ethyl alcohol；
The nickel salt is one or more of nickel chloride, nickel acetate or nickel nitrate；
Entitled 2,7- bis- (4- pyridines) -9-Fluorenone of the Fluorenone pyridine organic ligands, molecular formula C23H14N2O。
2. a kind of purposes of Fluorenone pyridine nickel nano-cluster as described in claim 1, which is characterized in that the Fluorenone pyridine nickel is received
Rice cluster is as effective catalyst catalysis carbon-carbon cross coupling reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838442A (en) * | 2012-08-09 | 2012-12-26 | 烟台万润精细化工股份有限公司 | 9-alkenylfluorene derivatives and application thereof |
| CN103396356A (en) * | 2013-08-12 | 2013-11-20 | 宁波大学 | Spirofluorene copper pyridine micro-nano particle and preparation method thereof |
| CN104628628A (en) * | 2015-02-05 | 2015-05-20 | 宁波大学 | Fluorene pyridine nickle nano-particles and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838442A (en) * | 2012-08-09 | 2012-12-26 | 烟台万润精细化工股份有限公司 | 9-alkenylfluorene derivatives and application thereof |
| CN103396356A (en) * | 2013-08-12 | 2013-11-20 | 宁波大学 | Spirofluorene copper pyridine micro-nano particle and preparation method thereof |
| CN104628628A (en) * | 2015-02-05 | 2015-05-20 | 宁波大学 | Fluorene pyridine nickle nano-particles and preparation method thereof |
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