CN107987015A - A kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application - Google Patents
A kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application Download PDFInfo
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- CN107987015A CN107987015A CN201711381611.5A CN201711381611A CN107987015A CN 107987015 A CN107987015 A CN 107987015A CN 201711381611 A CN201711381611 A CN 201711381611A CN 107987015 A CN107987015 A CN 107987015A
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- -1 pyridine radicals olefin Chemical class 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000013256 coordination polymer Substances 0.000 claims abstract description 31
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 31
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 11
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 238000011109 contamination Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- NXMFJCRMSDRXLD-UHFFFAOYSA-N 2-aminopyridine-3-carbaldehyde Chemical class NC1=NC=CC=C1C=O NXMFJCRMSDRXLD-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZDHKVKPZQKYREU-UHFFFAOYSA-N 4-(chloromethyl)pyridine;hydron;chloride Chemical class Cl.ClCC1=CC=NC=C1 ZDHKVKPZQKYREU-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- C07D213/04—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 having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—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 having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/27—Cadmium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application, wherein the chemical structural formula of asymmetric double pyridine radicals olefin(e) compounds is as follows：Preparation method technique of the present invention is simple, and reaction condition is gentle, and yield is high.1 (2 amino, 3 pyridine radicals) 2 (4 pyridine radicals) vinyl compound that the present invention synthesizes can be used as organic ligand to be self-assembly of coordination polymer [cadmium (1 (2 amino, 3 pyridine radicals) 2 (4 pyridine radicals) ethene) (5 nitro, 1,3 phthalic acid base)] with transition metal ionsn, cadmium coordination polymer stable structure in water, can be catalyzed light degradation organic dyestuff rhodamine B, make free of contamination CO2And H2O, and can recycled for multiple times.
Description
Technical field
The present invention relates to a kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application.
Background technology
In recent years, more pyridine compounds and theirs (for example, 4,4'-Bipyridine, phenanthroline etc.) and its coordination polymerization constructed
Thing is always one of hot subject of academic research.Pyridine compounds and their is nitrogenous heteroaromatic system, there is the pi bond of conjugation, pyrrole
Nitrogen-atoms in pyridine both can form coordinate bond with metal ion, can also form hydrogen bond.More pyridine compounds have multiple coordinations
Point, coordination mode is various, can form the coordination polymer of configurations.And such coordination polymer is because with charming topology knot
Structure and have broad application prospects in fluorescence, catalysis, absorption, magnetism and nonlinear optics etc. and receive multiple
The concern of section.
With the rapid development of modern industry and the rapid growth of population, water pollution be human society must face can not
The environmental problem avoided.Pollution of the organic dyestuff discharged from textile industry, printing and dyeing industry to water body is the main problem faced
One of.For many years, the mankind clear up the organic dyestuff in sewage using traditional physical absorption and biodegradation method always, still
These methods effect for most dyestuffs is unsatisfactory.Rhodamine B is one of common organic dyestuff of printing and dyeing industry, but sieve
Red bright B is difficult to be removed by biodegradation, it is also difficult to is cleared by physical absorption, particularly when sieve in polluted-water
When the bright B solubility of pellet is relatively low.Therefore, such organic dyestuff is converted into by innocuous substance by chemical reaction and seems particularly heavy
Will.The numerous studies of scientist prove：After adding suitable catalyst, through catalysis, light can effectively degrade in sewage
Organic dyestuff, makes it become nontoxic material.Such catalyst is all some semi-conducting materials, including：Metal oxide, metal
Sulfide, composite material and metal complex, they can serve as effective catalyst and green degraded carried out to organic dyestuff.
Coordination polymer causes the extensive concern of researcher as the effective catalyst of one of which, and constructs coordination polymer
Organic ligand the structure of coordination polymer and property that are self-assembly of are influenced it is very big.Therefore, complex functionality coordination is designed
Polymer is simultaneously developed into the effective catalyst of light degradation dyestuff and is one and significantly works.
The content of the invention
The present invention is intended to provide a kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application, pass through design
The asymmetric double pyridine radicals olefin(e) compounds of synthesis, and use it for assembling and prepare the catalysis light degradation of function coordination polymer having engine dyeing
Expect rhodamine B.
Asymmetric double pyridine radicals olefin(e) compounds of the invention are 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-second
Alkene, its chemical structural formula are as follows：
The preparation method of pyridine radicals olefin(e) compounds of the invention asymmetric double, including the preparation of intermediate, target product
Synthesize and isolate and purify each unit process：
Step 1：The preparation of intermediate
Using acetonitrile as solvent, by 4- chloromethyl pyridine hydrochlorides and triphenylphosphine mix and be refluxed reaction 3 it is small when, instead
Filtered after answering, obtain intermediate quaternary alkylphosphonium salt；
Reaction process is as follows：
Step 2：The synthesis of target product
In nitrogen atmosphere, stir lower slowly drop under conditions of ice-water bath by the dissolving of intermediate quaternary alkylphosphonium salt in methyl alcohol
Add the methanol solution of excessive sodium methoxide, the reaction was continued after dripping off, and half an hour generates phosphorus ylide, then removes ice-water bath, heats up
To room temperature, the methanol solution of 2- amino -3- pyridine carboxaldehydes is added dropwise under stirring into reaction solution, continues to stir at room temperature after dripping off
To Wittig, the reaction was complete within 5 hours for reaction；
In step 2, the molar ratio of intermediate quaternary alkylphosphonium salt, 2- amino -3- pyridine carboxaldehydes and sodium methoxide is 1:1:3.
Reaction process is as follows：
Step 3：Isolate and purify
The reaction solution revolving of step 2 is removed into solvent, adds water to stir, is extracted 2-3 times with dichloromethane, merge organic phase,
Revolving removes solvent and obtains the crude product of yellow；Crude product is washed with benzene, then with recrystallize with dichloromethane, you can obtain yellow
Target product.
The application of asymmetric double pyridine radicals olefin(e) compounds of the invention, is with asymmetric double pyridine radicals olefin(e) compounds
Coordination polymer is prepared as organic ligand and transition metal ions self assembly；The coordination polymer for [cadmium (1- (2- amino-
3- pyridine radicals) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids base)]n.N is number of repeat unit, is arbitrarily just
Integer.
Coordination polymer [cadmium (1- (2- amino -3- pyridines are prepared by asymmetric double pyridine radicals olefin(e) compounds
Base) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids base)]nThe step of it is as follows：
By 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene 1.97g, four nitric hydrate cadmium 3.08g, deionization
Water 80mL and 5- nitro -1,3- phthalic acid 2.11g is added in 150mL reaction kettles, when 170 DEG C of isothermal reactions 48 are small,
Then room temperature is slowly dropped to, the crystal of coordination polymer can be obtained.
The purposes of coordination polymer of the present invention, is the application when being catalyzed light degradation dye, rhodamine B as catalyst.
The application of coordination polymer of the present invention, is to be used when being catalyzed light degradation dye, rhodamine B as catalyst, makes it
Become free of contamination CO2And H2O, specifically comprises the following steps：
The rhodamine B solution that 20mL has just been prepared is taken in 100mL beakers, 1 drop hydrogen peroxide is added dropwise thereto, and add and match somebody with somebody
Position polymer irradiates solution, and be stirred continuously as catalyst with the xenon lamp of 350W.
The concentration of the rhodamine B solution is 0.005~3.00g/L.
The catalyst and the mass ratio of the rhodamine B are 1:(3~5).
Photodegradative reaction temperature is catalyzed as 10~50 DEG C, the reaction time is 60~200min.
The present invention is first by 4- chloromethyl pyridine hydrochlorides and triphenylphosphine reaction generation intermediate quaternary alkylphosphonium salt, intermediate season
After phosphonium salt and sodium alkoxide reaction generation phosphorus ylide, 2- amino -3- pyridine carboxaldehydes are added dropwise thereto immediately, is reacted and closed by Wittig
Into target product 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene.This preparation method technique is simple, reaction condition temperature
With yield height.1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-vinyl compound that the present invention synthesizes can be used as organic
Ligand is self-assembly of coordination polymer [cadmium (1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-second with transition metal ions
Alkene) (5- nitro -1,3- phthalic acids base)]n, cadmium coordination polymer stable structure in water, can be catalyzed light degradation organic dyestuff
Rhodamine B, makes free of contamination CO2And H2O, and can recycled for multiple times.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene；
Fig. 2 is [cadmium (1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids
Base)]nThe coordination mode figure of central metal cadmium；
Fig. 3 is [cadmium (1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids
Base)]nCrystal structure figure；
Fig. 4 is [cadmium (1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids
Base)]nTopology diagram；
Fig. 5 is the degradation rule curve map of rhodamine B.
Embodiment
Non-limiting examples of the present invention are stated as down：
4- chloromethyl pyridine hydrochlorides, 2- amino -3- pyridine carboxaldehydes, sodium methoxide, 5- nitro -1,3- phthalic acids base from
Shanghai lark waffle Technology Co., Ltd. purchases, rhodamine B, triphenylphosphine, acetonitrile, dichloromethane, methanol and N, N '-diformazan
Base formamide is purchased from Sinopharm Chemical Reagent Co., Ltd..
1st, the preparation of intermediate
By 4- chloromethyl pyridine hydrochlorides 16.40g (100mmol) and triphenylphosphine 28.85g (110mmol) in 100mL second
Be refluxed in nitrile reaction 3 it is small when, after reaction, be cooled to room temperature, filter, intermediate quaternary alkylphosphonium salt 39.65g, yield can be obtained
For 93%.
2nd, the preparation of target product
Sodium methoxide 6.75g (150mmol) is dissolved in 50mL methanol, the methanol solution of sodium methoxide is made.
2- amino -3- pyridine carboxaldehydes 6.11g (50mmol) are dissolved in 50mL methanol, 2- amino -3- pyridine carboxaldehydes are made
Methanol solution.
In nitrogen atmosphere, reaction bulb is placed in ice-water bath, intermediate quaternary alkylphosphonium salt 21.32g (50mmol) is dissolved in
In 50mL methanol, the methanol solution of just manufactured sodium methoxide is slowly added dropwise, rapid stirring, treats that the methanol solution of sodium methoxide is whole
After being added dropwise, continue stirring reaction half an hour generation phosphorus ylide, reaction recession makes reaction bulb anti-at room temperature from ice-water bath
Answer, the methanol solution of 2- amino -3- pyridine carboxaldehydes is added dropwise into the reaction bulb immediately, after solution is all added dropwise, in room
The lower stirring 5 of temperature makes Wittig when small, and the reaction was complete.
3rd, isolate and purify
Treat step 2 after reaction, reaction solution is evaporated with Rotary Evaporators, add the water of 50mL thereto, constantly stir
Mix, then with the extraction of 50mL dichloromethane three times, merge organic phase, dichloromethane is evaporated with Rotary Evaporators again, can be obtained
Flaxen crude product；50mL recrystallize with dichloromethane is used after washing crude product with 50mL benzene again, obtains target product 8.86g, is received
Rate is 86%.
Elemental analysis, hydrogen nuclear magnetic resonance have been carried out to product 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene
The characterization of spectrum.As a result it is as follows：
Elemental analysis (C12H11N3)：Theoretical value (%):C,73.07；H,5.62；N,21.30；Experiment value (%):C,
73.25；H,5.51；N,21.52.
1H NMR (400MHz, DMSO-d6) δ 8.52 (dd, J=4.4,1.6Hz, 2H), 7.92 (dd, J=4.8,1.6Hz,
1H), 7.81 (dd, J=7.6,1.6Hz, 1H), 7.63-7.57 (m, 3H), 7.07 (d, J=16.0Hz, 1H), 6.58 (dd, J=
7.6,4.8Hz,1H),6.29(s,2H).See Fig. 1.
4th, the preparation of coordination polymer
By 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene 1.97g (10mmol), 5- nitro -1,3- benzene two
Formic acid 2.11g (10mmol), four nitric hydrate cadmium 3.08g (10mmol) and deionized water (80mL) are added to 150mL reaction kettles
In, when 170 DEG C of isothermal reactions 48 are small, are down to room temperature after reaction, obtain light yellow crystal, crystal is taken out, spend from
Sub- water washing, then dries at room temperature, obtains the crystal 3.89g of coordination polymer, yield 82%.
Elemental analysis (C20H14N4O6Cd)：Theoretical value (%):C,46.31；H,2.72；N,10.80；Experiment value (%):C,
46.53；H,2.51；N,10.72.
The crystallographic parameter of coordination polymer：C20H15N3O4Cd,Mr=518.76, triclinic, space group α=103.52 (3) °, β=91.42 (3) °,
γ=114.86 (3) °, Z=2, Dc=1.781g cm-3, μ=1.177mm-1,18185reflections
measured,4421uniquereflections(Rint=0.0190), 4152observed reflections (I>2σ
(I)),280parameters,R1=0.0204, wR2=0.0512, S=1.095.
The coordination mode figure of cadmium metal is shown in Fig. 2, symmetric code in coordination polymer：(A):x+1,y+1,z；(B):-x,-y+
1,-z+2；
The x-ray crystal structure figure of coordination polymer is shown in Fig. 3；
The topology diagram of coordination polymer is shown in Fig. 4.
5th, coordination polymer catalysis light degradation rhodamine B
The rhodamine B of 0.15g is dissolved in prepare in the water of 1L and obtains rhodamine B solution, solubility 0.15g/L.
The rhodamine B solution that 20mL has just been prepared is taken in 100mL beakers, 1 drop hydrogen peroxide is added dropwise thereto, and add
The coordination polymer of 10mg, irradiates solution with the xenon lamp of 350W, and is stirred continuously.0.5mL was sampled every 15 minutes.By taking-up
After 0.5mL sample solutions are diluted to the solution of 5.0mL with deionized water, detect and find through ultraviolet-uisible spectrophotometer：Luo Dan
The concentration of bright B constantly reduces, and rhodamine B degraded is complete after 120 minutes, sees Fig. 5.Colourless solution ethyl acetate after degraded
Extraction, organic phase is by finding no the fragment of machine thing after gas chromatographic analysis, therefore, it is concluded that all organic dyestuff decompose
For CO2And H2O.After 5 circulations, catalytic effect is basically unchanged.
6th, contrast test
Its experimentation of the solution of a rhodamine B is separately taken to be catalyzed the experiment of light degradation rhodamine B with coordination polymer
Journey is similar, but does not add any catalyst thereto.Every sampling in 15 minutes once, detect and send out through ultraviolet-uisible spectrophotometer
It is existing：After 120 minutes, the concentration of rhodamine B varies less.See Fig. 5.
Claims (10)
1. a kind of asymmetric double pyridine radicals olefin(e) compounds, it is characterised in that its chemical structural formula is as follows：
2. the preparation method of the double pyridine radicals olefin(e) compounds of asymmetry described in a kind of claim 1, it is characterised in that including such as
Lower step：
Step 1：The preparation of intermediate
Using acetonitrile as solvent, by 4- chloromethyl pyridine hydrochlorides and triphenylphosphine mix and be refluxed reaction 3 it is small when, reaction knot
Filtered after beam, obtain intermediate quaternary alkylphosphonium salt；
Step 2：The synthesis of target product
In nitrogen atmosphere, it was slowly added dropwise under stirring under conditions of ice-water bath by the dissolving of intermediate quaternary alkylphosphonium salt in methyl alcohol
The methanol solution of the sodium methoxide of amount, the reaction was continued after dripping off, and half an hour generates phosphorus ylide, then removes ice-water bath, is warming up to room
Temperature, is added dropwise the methanol solution of 2- amino -3- pyridine carboxaldehydes into reaction solution under stirring, continue stirring reaction after dripping off at room temperature
To Wittig, the reaction was complete within 5 hours, and target product is obtained after isolating and purifying.
3. preparation method according to claim 2, it is characterised in that：
In step 2, described isolate and purify is that the reaction solution revolving of step 2 is removed solvent, adds water to stir, is extracted with dichloromethane
2-3 times, merge organic phase, revolving removes solvent and obtains the crude product of yellow；Crude product is washed with benzene, then is tied again with dichloromethane
It is brilliant, you can to obtain the target product of yellow.
4. preparation method according to claim 2, it is characterised in that：
In step 2, the molar ratio of intermediate quaternary alkylphosphonium salt, 2- amino -3- pyridine carboxaldehydes and sodium methoxide is 1:1:3.
A kind of 5. application of the double pyridine radicals olefin(e) compounds of asymmetry described in claim 1, it is characterised in that：Be with it is described not
Symmetric double pyridine radicals olefin(e) compound prepares coordination polymer as organic ligand and transition metal ions self assembly；The coordination
Polymer is [cadmium (1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene) (5- nitro -1,3- phthalic acids base)]n。
6. application according to claim 5, it is characterised in that include the following steps：
By 1- (2- amino -3- pyridine radicals) -2- (4- pyridine radicals)-ethene 1.97g, four nitric hydrate cadmium 3.08g, deionized water
80mL and 5- nitro -1,3- phthalic acids 2.11g is added in 150mL reaction kettles, when 170 DEG C of isothermal reactions 48 are small, so
After be slowly dropped to room temperature, the crystal of coordination polymer can be obtained.
A kind of 7. purposes of coordination polymer prepared by claim 5, it is characterised in that：The coordination polymer is in catalysis light drop
As catalyst application when solving dye, rhodamine B.
A kind of 8. application of coordination polymer prepared by claim 5, it is characterised in that：It is in catalysis light degradation dye, rhodamine
Used during B as catalyst, it is become free of contamination CO2And H2O, specifically comprises the following steps：
The rhodamine B solution that 20mL has just been prepared is taken in 100mL beakers, 1 drop hydrogen peroxide is added dropwise thereto, and add polycomplexation
Compound irradiates solution, and be stirred continuously as catalyst with the xenon lamp of 350W；The concentration of the rhodamine B solution for 0.005~
3.00g/L。
9. application according to claim 8, it is characterised in that：
The catalyst and the mass ratio of the rhodamine B are 1:(3~5).
10. application according to claim 8, it is characterised in that：
Photodegradative reaction temperature is catalyzed as 10~50 DEG C, the reaction time is 60~200min.
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| CN114716463A (en) * | 2022-05-17 | 2022-07-08 | 淮阴师范学院 | Photoresponse complex and preparation method and application thereof |
| CN114805185A (en) * | 2022-05-10 | 2022-07-29 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
| CN116120573A (en) * | 2022-12-19 | 2023-05-16 | 淮阴师范学院 | Coordination polymer material and preparation method and application thereof |
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| CN109761887A (en) * | 2019-01-29 | 2019-05-17 | 华南农业大学 | Degradation of organic dyes catalyst, composite catalyzing material and preparation method thereof |
| CN114805185A (en) * | 2022-05-10 | 2022-07-29 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
| CN114805185B (en) * | 2022-05-10 | 2023-09-19 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
| CN114716463A (en) * | 2022-05-17 | 2022-07-08 | 淮阴师范学院 | Photoresponse complex and preparation method and application thereof |
| CN114716463B (en) * | 2022-05-17 | 2024-02-06 | 淮阴师范学院 | Light response complex and preparation method and application thereof |
| CN116120573A (en) * | 2022-12-19 | 2023-05-16 | 淮阴师范学院 | Coordination polymer material and preparation method and application thereof |
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