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 PDF

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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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李妮娅
刘�东
马伟
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Huaibei Normal University
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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

A kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application
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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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
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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