CN106632027A - Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof - Google Patents
Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof Download PDFInfo
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- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910007566 Zn-MOF Inorganic materials 0.000 claims abstract description 30
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 20
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 10
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QBUQQUOGXPOBAQ-UHFFFAOYSA-N 3,5-dibromo-1-oxidopyridin-1-ium Chemical class [O-][N+]1=CC(Br)=CC(Br)=C1 QBUQQUOGXPOBAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- SOSPMXMEOFGPIM-UHFFFAOYSA-N 3,5-dibromopyridine Chemical class BrC1=CN=CC(Br)=C1 SOSPMXMEOFGPIM-UHFFFAOYSA-N 0.000 claims description 5
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 3,5- dibromo pyridines 3,5- dibromo pyridine-N- oxides Chemical class 0.000 claims description 4
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 150000003222 pyridines Chemical class 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GHXRKGHKMRZBJH-UHFFFAOYSA-N boric acid Chemical compound OB(O)O.OB(O)O GHXRKGHKMRZBJH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- 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
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a metal organic frame based on a pyridine oxide ligand, and a preparation method and application thereof. The structural formula of the metal organic frame Zn-MOF is (ZnLBr2)n, wherein L refers to the pyridine oxide ligand L with the structural formula shown as below, and n refers to a non-zero natural number. A preparation method of the pyridine oxide ligand L includes (1), preparing 3, 5-dihalogenated pyridine into 3, 5-dihalogenated pyridine-N-oxide; (2), subjecting the 3, 5-dihalogenated pyridine-N-oxide to Suzuki reaction to obtain the pyridine oxide ligand L. According to the preparation method of the metal organic frame based on the pyridine oxide ligand, ZnBr2 liquor is laid on pyridine oxide ligand L liquor, and standing is performed to obtain a colorless monocrystal, namely the metal organic frame Zn-MOF. When the metal organic frame serves as a catalyst, reaction temperature is mild, reaction time is short, activity is high, catalyst consumption is low, the catalyst is easy to recycle, catalyst utilization rate is increased, and cost is reduced.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of metal based on pyridine oxide part has machine frame
Frame and preparation method and application.
Background technology
The dehydration condensation of aldehydes or ketones and activity methene compound, the reaction for forming carbon-carbon double bond is referred to as
Knoevenagel condensation reactions.Such reaction can be directly synthesized a large amount of useful compounds, in industry, agricultural, pharmacy, life
The numerous areas extensive application such as thing science.Knoevenagel condensation reactions are usually sour with Lewis or alkali is catalyst,
Also catalyst can be made using weak base (amine, pyridine etc.), is reacted in homogeneous or out-phase environment, the commonly required time is longer,
And yield is relatively low.
Metal-organic framework materials (Metal-OrganicFrameworks, MOFs) are class I organic-inorganic hybridized materials
Material, is formed by organic ligand and inorganic metal cell formation.Typically there is changeable topological structure and physicochemical properties.With
Traditional porous material is compared, and MOFs has larger specific surface area and framework internal pore volume, is existed as a class functionalization material
Catalysis aspect shows very big advantage.
But existing metal organic frame as the problem that a kind of lewis acid catalyst is present have stability it is poor, prepare step
It is rapid it is loaded down with trivial details, activity is low, can not reclaim.
The content of the invention
To overcome the defect of prior art, the invention provides a kind of metal organic frame based on pyridine oxide part and
Preparation method and application.
For achieving the above object, the technical scheme is that：
A kind of pyridine oxide ligand L, wherein, the chemical structural formula of L is：
The preparation method of above-mentioned pyridine oxide ligand L, (1) by 3,5- dihalopyridines be prepared into 3,5- dihalopyridines-
3,5- dihalopyridine-N- oxides are obtained pyridine oxide ligand L by N- oxides, (2) through Suzuki coupling reactions.
The Suzuki coupling reactions are also referred to as suzuki reaction, are a newer organometallic coupling reactions, and zeroth order palladium is matched somebody with somebody
Under compound catalysis, aryl, pyridine or ene boric acid (borate) occur to intersect occasionally with chlorine, bromine, iodo aromatic hydrocarbon (pyridine or alkene)
Connection.
The structural formula of 3,5- dihalopyridines is：
Wherein, R is halo groups, such as Cl, Br.
The structural formula of 3,5- dihalopyridine-N- oxides is：
Wherein, R is halo groups, such as Cl, Br.
Preferably, 3,5- dibromo pyridines are prepared into 3,5- dibromo pyridines-N- oxidations by (1) using metachloroperbenzoic acid
3,5- dibromo pyridine-N- oxides and 4- pyridine boronic acids are obtained pyridine oxide ligand L by thing, (2) through Suzuki coupling reactions.
Preferably, the solvent that step (1) is adopted is for tetrahydrofuran.
Preferably, the reaction condition in step (1) is：48h is stirred at normal temperatures.
It is further preferred that 3,5- dibromo pyridines and the mol ratio of metachloroperbenzoic acid are 1 in step (1):2.50～
3.00。
Still more preferably, 3,5- dibromo pyridines and the mol ratio of metachloroperbenzoic acid are 1 in step (1):2.96.
Preferably, the catalyst that step (2) is adopted is for tetrakis triphenylphosphine palladium.
Preferably, the reaction condition of step (2) is：It is heated to reflux 48 hours, is heated to reflux temperature for 75-80 DEG C.
Preferably, 3,5- dibromo pyridine-N- oxides and the mol ratio of 4- pyridine boronic acids are 1 in step (2):2.2～
2.5。
It is further preferred that 3,5- dibromo pyridine-N- oxides and the mol ratio of 4- pyridine boronic acids are 1 in step (2):
2.4。
Preferably, the alkali for adopting in the Suzuki coupling reactions is for K2CO3。
It is further preferred that 3,5- dibromo pyridine-N- oxides and K in step (2)2CO3Mol ratio be 1:12.5.
A kind of metal organic frame Zn-MOF, its structural formula is (ZnLBr2)n, wherein, L be above-mentioned pyridine oxide ligand L, n
For the natural number of non-zero.
Preferably, the metal organic frame is monoclinic system, belongs to P2 (1)/n space groups.
It is further preferred that the metal organic frame has a kind of Zn (II) center, it is in (ZnN2Br2) coordination
In environment, and the nitrogen-atoms of Zn (II) coordinations come from the end group pyridine of ligand L, and Zn-N key lengths are respectivelyWithWherein, the oxygen of pyridine oxide has neither part nor lot in coordination in ligand L, and Zn (II) is centrally through matching somebody with somebody
The pyridine nitrogen atom of body end is connected, and along b direction of principal axis one dimensional helical chain is stretched to；Oxygen atom on one chain on pyridine oxide and
Hydrogen atom on an other chain on pyridine oxide forms hydrogen bond, and above-mentioned one dimensional helical chain is further connected as ripple by these hydrogen bonds
The chiral two-dimensional surface of wave-like.
Still more preferably, the most short distance between two Zn (II) is
A kind of preparation method of metal organic frame Zn-MOF, by ZnBr2Solution is layered on above-mentioned pyridine oxide ligand L solution
On, colorless single-crystal is obtained after standing and is metal organic frame Zn-MOF.
Preferably, the ZnBr2Solvent in solution is methanol.
Preferably, the ZnBr2ZnBr in solution2Concentration be 0.005mol/L.
Preferably, the solvent of the pyridine oxide ligand L solution is dichloromethane.
Preferably, the concentration of pyridine oxide ligand L is 0.005mol/L in the pyridine oxide ligand L solution.
Preferably, ZnBr2It is 1 with the input mol ratio of pyridine oxide ligand L:1.
Preferably, preparation temperature is room temperature.
Heretofore described room temperature is 15-25 DEG C.
A kind of applications of above-mentioned metal organic frame Zn-MOF in catalysis Knoevenagel condensation reactions.
A kind of catalyst, including above-mentioned metal organic frame Zn-MOF.
A kind of synthetic method of benzyl allyl dintrile, with benzaldehyde and Cyanoacetyl-Cyacetazid as raw material, with above-mentioned metal organic frame Zn-
MOF is catalyst, and after reacting at room temperature benzyl allyl dintrile is obtained final product.
Preferably, the mol ratio of the benzaldehyde and Cyanoacetyl-Cyacetazid is 1:1.2.
Preferably, its step is to add catalyst after benzaldehyde and Cyanoacetyl-Cyacetazid are mixed into a period of time, continues to stir
After a period of time, you can obtain benzyl allyl dintrile.
Preferably, the benzaldehyde and the mol ratio of catalyst are 1:0.04.
A kind of recovery methods of above-mentioned metal organic frame Zn-MOF after catalysis Knoevenagel condensation reactions,
After Knoevenagel condensation reactions, metal organic frame Zn-MOF is reclaimed by being centrifuged to mixed liquor.
Beneficial effects of the present invention：
(1) it is catalyzed using the Zn-MOF of the present invention, is realized heterocatalysis, while the Zn-MOF stability for preparing
It is good, can reuse more than five times, and catalyst reclaims easy, improves the utilization rate of catalyst, reduces cost.
(2) reaction temperature of the invention is gentle, and the response time is shorter, and activity is high, and catalyst amount is few, without other additions
Agent.
Description of the drawings
Fig. 1 is the pyridine oxide ligand L of the embodiment of the present invention 11HNMR；
Fig. 2 is the infrared spectrum of the pyridine oxide ligand L of the present invention；
Fig. 3 is the infrared spectrum of the Zn-MOF of the present invention；
Fig. 4 is the TGA spectrograms of the Zn-MOF of the present invention；
Fig. 5 is mono-crystalline structures figure, one-dimensional catenary structure and the chiral two-dimensional surface structure of the Zn-MOF of the present invention, wherein, A is
The mono-crystalline structures figure of the present invention, B is one-dimensional catenary structure figure of the present invention, and C is present invention chirality two-dimensional surface structure chart；
Fig. 6 is corresponding PXRD spectrograms of the Zn-MOF of the present invention after catalysis Knoevenagel condensation reactions.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.
Embodiment 1：The preparation of pyridine oxide ligand L
Specific preparation process is as follows：
(1) in 250mL single port bottles, 3,5- dibromo pyridines (3.2g, 13.5mmol) are dissolved in into 50mL THF, add m-chloro
Benzoyl hydroperoxide (6.88g, 40mmol), is stirred at room temperature 48 hours, and reaction adds saturated aqueous sodium carbonate 30mL after terminating, quiet
Layering is put, water is mutually with 2 × 50mL CH2Cl2Extraction, merges organic faciess and uses anhydrous Na2SO4It is dried, silica gel column chromatography (CH2Cl2)
Obtain shallow white solid 1.53g, as 3,5- dibromo pyridine-N- oxides, yield 44.1%.1H NMR(300MHz,DMSO,25
℃,TMS):δ=8.60 (s, 2H ,-C5H3NBr2),7.97(s,1H,-C5H3NBr2)。
(2)N2Under protection, 3,5- dibromo pyridines-N- oxides (2.53g, 10.0mmol), 4- pyridine boronic acids (2.95g,
24.0mmol), four triphenyl phosphorus close palladium (1.16g, 1.0mmol), Anhydrous potassium carbonate (17.25g, 125.0mmol), ethanol
In there-necked flask, 75 DEG C of temperature control stirs 48h for 60mL, water 60mL.Remove solvent under reduced pressure, wash, vacuum drying, column chromatography
(CH2Cl2:CH3OH=20:1) white powder, as pyridine oxide ligand L, are obtained.
Pyridine oxide ligand L to obtaining carries out the sign of proton nmr spectra and infrared spectrum, and its result is as respectively such as
Fig. 1, shown in 2.
Embodiment 2：The synthesis of Zn-MOF
At room temperature, by ZnBr2(2.2mg, 0.01mmol) is dissolved in methanol (2mL) and obtains ZnBr2Methanol solution, by L
(2.4mg, 0.01mmol) is dissolved in CH2Cl2In solution (2mL), methanol solution is slowly layered on CH2Cl2On solution, three days are stood
After obtain colorless single-crystal.
By infrared spectrum (IR), thermogravimetric analysiss spectrogram (TGA) characterizes the compound, and Fig. 3, Fig. 4 are as a result seen respectively.
Zn-MOF mono-crystalline structures are as shown in Figure 5.
As seen from Figure 5, Zn-MOF is monoclinic system, belongs to P2 (1)/n space groups.A kind of Zn is only existed in Zn-MOF
(II) center, it is in (ZnN2Br2) coordination environment in, and the nitrogen-atoms that it is coordinated come from the end group pyridine of ligand L,
Zn-N key lengths are respectivelyWithWherein, the oxygen of pyridine oxide has neither part nor lot in and matches somebody with somebody in ligand L
Position, Zn (II) is connected centrally through the pyridine nitrogen atom of part end, and along b direction of principal axis one dimensional helical chain is stretched to.On one chain
Hydrogen atom on oxygen atom and an other chain on pyridine oxide on pyridine oxide forms hydrogen bond, and these hydrogen bonds will be above-mentioned one-dimensional
Coiled strand is further connected as wavy chiral two-dimensional surface.Most short distance between Zn (II) and Zn (II) isTool
Body crystal data is shown in Table 1
The crystallographic data of the Zn-MOF of table 1
Experimental example 3：Benzaldehyde is generated with Cyanoacetyl-Cyacetazid condensation reaction
Under room temperature, benzaldehyde (1mmol) and Cyanoacetyl-Cyacetazid (1.2mmol) are added in 2mL vials, after stirring 5 minutes, plus
Enter catalyst Z n-MOF (19mg, 4% (mol), on the basis of the amount of benzaldehyde), continue to stir 6h, follow the trail of anti-with gas chromatogram
Should, after reaction terminates, quick centrifugation, the solid after centrifugation is as used for the catalyst Z n-MOF of catalytic reaction, reclaims catalyst,
Subsequent cycle reaction is direct plungeed into, according to above-mentioned condition, catalyst is calculated by gas chromatogram and produced using 5 circulations, reactant liquor
Rate, as shown in table 2, the catalyst of recovery is characterized catalytic effect by PXRD, as shown in Figure 6.
The yield and TOF values of the Zn-MOF of table 2 catalysis Knoevenagel 5 circulations of condensation reaction
a:Yield determines b by GC:TOF=%yield (mmol of substrate/mmol of cat.h)
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to invention protection domain
Restriction, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
The various modifications or deformation made by paying creative work are still within the scope of the present invention.
Claims (10)
1. a kind of pyridine oxide ligand L, is characterized in that, the chemical structural formula of L is：
2. the preparation method of pyridine oxide ligand L as claimed in claim 1, is characterized in that, (1) is by 3,5- dihalopyridine systems
For into 3,5- dihalopyridine-N- oxides, 3,5- dihalopyridine-N- oxides are obtained oxygen by (2) through Suzuki reactions
Change pyridine ligand L.
3. preparation method as claimed in claim 2, is characterized in that, (1) is using metachloroperbenzoic acid by 3,5- dibromo pyridines
3,5- dibromo pyridine-N- oxides are prepared into, (2) are by 3,5- dibromo pyridine-N- oxides and 4- pyridine boronic acids through Suzuki
Reaction obtains pyridine oxide ligand L；
Preferably, 3,5- dibromo pyridines and the mol ratio of metachloroperbenzoic acid are 1 in step (1):2.50～3.00；
Preferably, 3,5- dibromo pyridine-N- oxides and the mol ratio of 4- pyridine boronic acids are 1 in step (2):2.2～2.5.
4. a kind of metal organic frame Zn-MOF, is characterized in that, structural formula is (ZnLBr2)n, wherein, L is described in claim 1
Pyridine oxide ligand L, n for non-zero natural number.
5. metal organic frame Zn-MOF as claimed in claim 4, is characterized in that, the metal organic frame is monoclinic crystal
System, belongs to P2 (1)/n space groups；
Preferably, there is a kind of Zn (II) center in the metal organic frame, and it is in (ZnN2Br2) coordination environment in, and Zn
(II) nitrogen-atoms of coordination come from the end group pyridine of ligand L, and Zn-N key lengths are respectivelyWithWherein, the oxygen of pyridine oxide has neither part nor lot in coordination in ligand L, Zn (II) centrally through part end pyridine nitrogen
Atom is connected, and along b direction of principal axis one dimensional helical chain is stretched to；Oxygen on oxygen atom and an other chain on one chain on pyridine oxide
Change the hydrogen atom on pyridine and form hydrogen bond, above-mentioned one dimensional helical chain is further connected as wavy chiral two dimension by these hydrogen bonds
Face；
It is further preferred that the most short distance between two Zn (II) is
6. a kind of preparation method of metal organic frame Zn-MOF, is characterized in that, by ZnBr2Solution is layered on described in claim 1
On pyridine oxide ligand L solution, colorless single-crystal is obtained after standing and is metal organic frame Zn-MOF；
Preferably, the ZnBr2ZnBr in solution2Concentration be 0.005mol/L；
Preferably, the concentration of pyridine oxide ligand L is 0.005mol/L in the pyridine oxide ligand L solution；
Preferably, ZnBr2It is 1 with the input mol ratio of pyridine oxide ligand L:1.
7. the metal organic frame Zn-MOF described in a kind of claim 4 or 5 catalysis Knoevenagel condensation reactions in should
With.
8. a kind of catalyst, is characterized in that, including the metal organic frame Zn-MOF described in claim 4 or 5.
9. a kind of synthetic method of benzyl allyl dintrile, is characterized in that, with benzaldehyde and Cyanoacetyl-Cyacetazid as raw material, with claim 4 or 5
Described metal organic frame Zn-MOF is catalyst, and after reacting at room temperature benzyl allyl dintrile is obtained final product；
Preferably, the mol ratio of the benzaldehyde and Cyanoacetyl-Cyacetazid is 1:1.2；
Preferably, its step is to add catalyst after benzaldehyde and Cyanoacetyl-Cyacetazid are mixed into a period of time, continues to stir one section
After time, you can obtain benzyl allyl dintrile.
10. the metal organic frame Zn-MOF described in a kind of claim 4 or 5 is after catalysis Knoevenagel condensation reactions
Recovery method, is characterized in that, after Knoevenagel condensation reactions, have machine frame to metal by being centrifuged to mixed liquor
Frame Zn-MOF is reclaimed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195531A (en) * | 2020-01-20 | 2020-05-26 | 安徽师范大学 | Hybrid material of multi-pyridine zinc complex modified MIL-101, preparation method and application of hybrid material in catalyzing degradation of organic phosphorus |
| CN112745261A (en) * | 2020-02-27 | 2021-05-04 | 广东聚华印刷显示技术有限公司 | Electron transport material, method for producing the same, electronic device, and display device |
| CN113402720A (en) * | 2021-05-17 | 2021-09-17 | 山东师范大学 | Pyridine oxide COF material and preparation method and application thereof |
-
2016
- 2016-12-16 CN CN201611168895.5A patent/CN106632027A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| JUN-YAN CHENG等: ""Synthesis, Structure, and Ligand-Centered Catalytic Properties of MII Coordination Polymers (M=ZnII, CdII, HgII)with Open Pyridyl N-Oxide Sites"", 《CHEMPLUSCHEM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195531A (en) * | 2020-01-20 | 2020-05-26 | 安徽师范大学 | Hybrid material of multi-pyridine zinc complex modified MIL-101, preparation method and application of hybrid material in catalyzing degradation of organic phosphorus |
| CN111195531B (en) * | 2020-01-20 | 2022-08-02 | 安徽师范大学 | Hybrid material of multi-pyridine zinc complex modified MIL-101, preparation method and application of hybrid material in catalyzing degradation of organic phosphorus |
| CN112745261A (en) * | 2020-02-27 | 2021-05-04 | 广东聚华印刷显示技术有限公司 | Electron transport material, method for producing the same, electronic device, and display device |
| CN113402720A (en) * | 2021-05-17 | 2021-09-17 | 山东师范大学 | Pyridine oxide COF material and preparation method and application thereof |
| CN113402720B (en) * | 2021-05-17 | 2022-11-29 | 山东师范大学 | Pyridine oxide COF material and preparation method and application thereof |
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