CN104017004A - 1:2 type enol-form pyridine metal complexes and preparation method and application thereof - Google Patents
1:2 type enol-form pyridine metal complexes and preparation method and application thereof Download PDFInfo
- Publication number
- CN104017004A CN104017004A CN201410262368.5A CN201410262368A CN104017004A CN 104017004 A CN104017004 A CN 104017004A CN 201410262368 A CN201410262368 A CN 201410262368A CN 104017004 A CN104017004 A CN 104017004A
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction
- enol form
- add
- pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention provides a synthesis method and application of 1:2 type enol-form pyridine metal complexes. The 1:2 type enol-form pyridine metal complexes are a series of metal complexes synthesized by taking a ligand coordinated with enol-form pyridine as a transfer reagent which acts with the alkylation reagents of magnesium, aluminum and zinc; the kind of enol-form pyridine metal complexes can be used for crystallizing the ring opening polymerization of aliphatic lactone. The synthesis method of the complexes provided by the invention is simple, the requirements for the conditions are relatively low, and the yield is relatively high; the synthesized complexes have good catalytic activity and relatively high selectivity on the ring opening polymerization of lactone. Due to the good biocompatibility and low toxicity of the kind of catalysts, the enol-form pyridine metal complexes can be perfectly applied to the catalytic synthesis of biodegradable polyester materials.
Description
Technical field
The present invention relates to catalyst preparation technical field, be specifically related to monokaryon metal complexes of a class [N, O] bitooth ligand and aluminium, magnesium and zinc coordination and preparation method thereof, this metal complexes can be used as synthetic fat adoption ester catalysts.
Background technology
Aliphatic polyester is used widely in the field such as medical, industrial, agriculture as a kind of Biodegradable material, and it also has good biocompatibility and avirulent advantage except having high molecular feature, has become the focus of Material Field research.At present, the ring-opening polymerization of cyclic ester and lactide has more advantages with respect to polycondensation, and as mild condition, monomer conversion is high, the polymkeric substance that the high molecular that is easy to get and molecular weight are narrow etc., and become the most deep method of research now.Used catalyst mainly contains aluminium system, zinc system, magnesium system, calcium system and tin system etc.This patent mainly provides the synthetic method of zinc monokaryon catalyzer.
Aluminum-based catalyst
Last century, the tetraphenylporphyrin aluminium alkyl oxide of the eighties report was early attempting of controlled catalysis ring-opening polymerization to the research of cyclic ester monomer ring-opening polymerization, the polyester that this catalyst system catalysis forms has molecular weight can be predicted, the feature of narrow molecular weight distribution.In addition, Schiff bases is similar to porphyrin and has the synthetic simple and strong advantage of part Scalability, and is widely studied.2005, NobuyoshiNomura study group reported a series of salicylyl imines class aluminum compounds, the ε-hexamethylene of catalysis quickly and efficiently lactone ring opening polymerization.Also have the research recently of some aluminum alkoxide catalyzer more.
Zinc-magnesium series catalysts
N, the metallic zinc title complex of O coordination is the simple part of a class of studying early, is also the more class part of research.The people such as Tolman in 2003 have reported class amido phenols Zn (II) complex compound, and such catalyzer can cause the controlled ring-opening polymerization of rac-Lactide fast, can obtain the polymerization product of the high and narrowly distributing of molecular weight.Salen type N, the metallic zinc compound of O coordination is the widest class of research in cyclic esters ring-opening polymerization catalysis zinc system, its rac-Lactide of catalysis efficiently Jian cyclopolymerization, and the feature of embodiment living polymerization.2010, the people such as Hayes obtained cationic Zn complex, catalysis rac-lactide polymerization efficiently, and resulting polymers also has certain stereoselectivity.
Magnesium and zinc are all similar aspect a lot of attributes, but Mg is often regarded as hard metal, Zn is soft metal, manyly for the organic ligand of stablizing Zn (II), can form stable and have a catalyzer of catalysis cyclic esters ring-opening polymerization activity with Mg (II) complexing too.Magnesium does not almost have toxicity concerning organism, and compares with aluminium, zinc catalyst, and the activity of Mg catalyst is generally higher, so come catalysis or initiation cyclic esters ring-opening polymerization with magnesium complex, is the focus that people study always.
Magnesium, aluminium, zinc class catalyzer are the focus of research because its toxicity is little, and itself just can be for catalyzed polymerization.Up to the present, what discovery catalysis LA ring-opening polymerization effect was best is zinc lactate, can better control the molecular weight of polymkeric substance, and simple title complex is unstable, therefore designs part and makes title complex more stable so that apply extremely important.
Summary of the invention
The object of the present invention is to provide the application as catalyzer in aliphatic ester ring-opening polymerization of a kind of magnesium, zinc and aluminum complex of 1:2 type enol form pyridine coordination and synthetic and this metal complexes thereof.
The invention provides a kind of 1:2 type enol form pyridinium metal complex, its structural formula is:
Wherein: R
1=H, CH
3
R
2＝CH
3,Ar,Bu
t
M=Mg, R '=Bu, n=2 or M=Zn, R '=Et, n=2 or M=Al, R '=Me, n=3.
Its synthetic method, comprises the steps:
(1) in anhydrous and oxygen-free condition, under ice bath, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-alkyl pyridine, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 ℃, the nitrile with 2-alkyl pyridine equimolar amount is dropwise added in reaction solution, react after half an hour, recover room temperature and continue reaction approximately 2 days, obtain brown solution;
At 0 ℃, in above-mentioned solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath stir about 1 day, add saturated NaOH to neutralize, until pH value is 7-8, now produce white Na
2sO
4precipitation, adds distilled water to solution to clarify; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removes methylene dichloride, in the underpressure distillation of 5mmHg pressure, collects cut, obtains enol form pyridine ligand;
(2) the enol form pyridine ligand and the MR ' that by mol ratio, are 2:1
nbe dissolved in respectively in normal hexane solvent, at 0 ℃, the hexane solution of enol form pyridine ligand dropwise added to MR '
nhexane solution in, the reaction deicing of dropping back half an hour is bathed, and rises to gradually room temperature and continues at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, adds normal hexane washing precipitation, standing, remove by filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
Another kind of 1:2 type enol form pyridinium metal complex provided by the invention, its structural formula is:
Wherein: R
1=Ph
R
2＝CH
3,Ar,Bu
t
M=Mg, R '=Bu, n=2 or M=Zn, R '=Et, n=2 or M=Al, R '=Me, n=3.
Its synthetic method, comprises the steps:
(1) in anhydrous and oxygen-free condition, under ice bath, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-benzyl-pyridine, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 ℃, the nitrile with 2-benzyl-pyridine equimolar amount is dropwise added in reaction solution, react after half an hour, recover room temperature and continue reaction approximately 2 days, obtain brown solution;
At 0 ℃, in above-mentioned solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath stir about 1 day, add saturated NaOH to neutralize, until pH value is 7-8, now produce white Na
2sO
4precipitation, adds distilled water to solution to clarify; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removes methylene dichloride, in the underpressure distillation of 5mmHg pressure, collects cut, obtains enol form pyridine ligand;
(2) the enol form pyridine ligand and the MR ' that by mol ratio, are 2:1
nbe dissolved in respectively in normal hexane solvent, at 0 ℃, the hexane solution of enol form pyridine ligand dropwise added to MR '
nhexane solution in, the reaction deicing of dropping back half an hour is bathed, and rises to gradually room temperature and continues at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, adds normal hexane washing precipitation, standing, remove by filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
Enol form pyridine magnesium, aluminium, zinc metal complexes prepared by the present invention can be used as catalyzer, are used in conjunction with initiator benzylalcohol or Virahol, for ε-hexamethylene lactone ring opening polymerization, react.
Compared with prior art, advantage of the present invention:
The present invention is by changing substituent R 1 and R2, obtain having the part of different spaces steric hindrance and electronic effect, and then generation has the title complex of different electronic effects and steric effect, preparation method is simple, conditional request is relatively low, and productive rate is relatively high, the title complex obtaining is used for catalysis ring-opening polymerization.It is little that such catalyzer has toxicity, the good and catalytic activity high of biocompatibility, the polyester material that available energy is good.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of embodiment 1
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of embodiment 2
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of embodiment 3
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of embodiment 4
Fig. 5 is the nucleus magnetic hydrogen spectrum figure of embodiment 5
Embodiment
To respond be all to carry out under the high pure nitrogen of crossing through potassium post drying treatment or argon shield, use the reaction technology operation of standard.
Embodiment 1: the preparation of part 2-(4'-butanone base)-pyridine
Under nitrogen atmosphere, 2-picoline (2.97g, 31.96mmol) is added in 250mL reaction flask, add the tetrahydrofuran (THF) that about 100mL is dry, stir it is fully dissolved.Under condition of ice bath, with syringe, dropwise add n-Butyl Lithium 25.56mL (2.5M, 63.92mmol), react the deicing of dropping back half an hour and bathe recovery stirring at room 3h, obtain dark red solution.
In nitrogen protection, cryosel is bathed under (40 ℃) condition and is got acetonitrile (1.66mL, 31.96mmol) and be dropwise added in previous step reaction flask with syringe, and reaction recovers stirring at room 2 days after half an hour, obtains brown solution.
Under condition of ice bath, to the sulphuric acid soln that adds 60% in reaction solution, carry out acid hydrolysis, treat that pH reaches till 1, react 1 day, solution colour becomes chocolate.Under condition of ice bath, add in saturated sodium hydroxide and excessive sulphuric acid soln, the solid that dissolves generation with a large amount of distilled water is until solution clarification.In solution, add dichloromethane extraction three times, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, remove methylene dichloride, in the underpressure distillation of 5mmHg pressure, collect 75 ℃ of cuts (vacuum tightness is 0.85-0.90MPa), obtain glassy yellow oily matter 2-(4'-butanone base)-pyridine.Productive rate: 32.28%.1H NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=2.11 (s, 3H,-CH3), 3.89 (s, 2H,-CH2), 7.26 (m, 2H, four, five position of pyridine), 7.70 (m, 1H, three position of pyridine), 8.46 (d, J=3.9,1H, six position of pyridine) .13C NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=34.17 (CH3), 57.35 (CH2); 126.99,129.46,141.68,154.25,160.46 (pyridineC), 210.46 (C=O), are specifically shown in Fig. 1.
Embodiment 2: the preparation of part 2-(2'-phenacyl)-pyridine
Under nitrogen atmosphere, get 2-picoline (2.86g, 30.73mmol) and be injected in 250mL reaction flask, add the tetrahydrofuran (THF) that about 100mL is dry, stir it is fully dissolved.Under condition of ice bath, dropwise add n-Butyl Lithium 25.56mL (2.5M, 61.46mmol), react the deicing of dropping back half an hour and bathe recovery stirring at room 3h, obtain dark red solution.
Under nitrogen protection, cryosel bath (40 ℃) condition, get cyanophenyl (3.15mL, 30.73mmol) and be dropwise added in previous step reaction flask, ice bath reacts the deicing of dropping back half an hour and bathes recovery stirring at room 2 days, obtains brown-red solution.
The reaction that is hydrolyzed under condition of ice bath, to the sulphuric acid soln (about 30mL) that adds a certain amount of 60% in reaction flask, treats that pH reaches till 1, reacts 1 day, and solution colour becomes chocolate.Under condition of ice bath, add in saturated sodium hydroxide and excessive sulphuric acid soln, the solid that dissolves generation with a large amount of distilled water is until solution clarification.In solution, add dichloromethane extraction three times, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, remove methylene dichloride, in the underpressure distillation of 5mmHg pressure, collect 135 ℃ of cuts (vacuum tightness is 0.85-0.90MPa), obtain yellow oil product, because being easy to solidify, product becomes subsequently yellow solid 2-(2'-phenacyl)-pyridine, productive rate: 30.73%.1H NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=4.54 (s, 1H,-CH), 6.37-8.47 (m, 9H, benzen and pyridine), 15.38 (s, 1H, N-H of pyridine) .13C NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=48.55 (CH); 94.69,119.93,122.78,126.03,129.63,130.15,138.90,145.17,149.96 (benzenC and pyridineC), 197.96 (C=O), are specifically shown in Fig. 2.
Embodiment 3: the preparation of part 2-(2'-o-methyl-benzene ethyl ketone base)-pyridine
Under nitrogen atmosphere, with syringe, get 2-picoline (2.89g, 31.08mmol) and be injected in 250mL reaction flask, add the tetrahydrofuran (THF) that 100mL is dry that it is fully dissolved.Under condition of ice bath, dropwise add n-Butyl Lithium 24.86mL (2.5M, 62.17mmol), react the deicing of dropping back half an hour and bathe recovery stirring at room 3h, obtain dark red solution.
In nitrogen protection, cryosel is bathed under (40 ℃) condition and is also dropwise added in previous step reaction flask with getting o-methyl-benzene nitrile (3.68mL, 31.08mmol), and ice bath reacts the deicing of dropping back half an hour and bathes recovery stirring at room 2 days, obtains dark red solution.
The reaction that is hydrolyzed under condition of ice bath, to the sulphuric acid soln that adds 60% in reaction flask, all dissolves all precipitations and pH value reaches 1.Remove ice bath room temperature reaction 1 day, obtain dark solution.Under ice bath, slowly drip saturated sodium hydroxide solution neutralisation of sulphuric acid, add subsequently distilled water dissolution precipitation to solution to clarify, in solution, add dichloromethane extraction three times, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removes methylene dichloride, in the underpressure distillation of 5mmHg pressure, collect 138 ° of C cuts (vacuum tightness is 0.85-0.90MPa), obtain yellowish red color oily matter.Subsequently, post is further purified excessively, and (eluent ratio is: sherwood oil: ethyl acetate=10:1), obtain faint yellow oily part 2-(2'-o-methyl-benzene ethyl ketone base)-pyridine, productive rate: 39.15%.1H NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=2.40 (s, 3H ,-CH3of benzen), 7.11-8.49 (m, 8H, H of benzen and pyridine), 15.25-15.38 (s, 1H, N-H of pyridine) .13C NMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=19.67 (CH3), 49.73 (CH); 96.66,118.16,120.87,123.79,125.00,127.32,128.07,130.01,135.83,143.30,148.44 (benzenC and pyridineC), 200.19 (C=O), are specifically shown in Fig. 3.
Embodiment 4: the preparation of enol form pyridine Metal Zn title complex
Under nitrogen atmosphere, get part 2-(2'-phenacyl)-pyridine (0.51g, 2.57mmol) in the reaction flask being dried, in part, add appropriate normal hexane solvent, abundant stirring and dissolving, getting zinc ethyl 1.28mL (1M, 1.28mmol) is dissolved in appropriate normal hexane solvent again.At 0 ℃, the hexane solution of part is slowly added drop-wise in zinc ethyl solution, there is immediately precipitation, ice bath returns to stirring at room reaction 3h after half an hour, obtain the turbid liquid of deep yellow, standing and reacting spend the night after upper strata for approaching colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow Metal Zn title complex (4).1H NMR (CDCl3, TMS, 300MHz): δ (ppm)=5.921 (s, 1H ,-CH-), 6.782-7.052 (m, 9H, benzenH and pyridineH), is specifically shown in Fig. 4.
Embodiment 5: the preparation of enol form pyridine metal Al title complex
Under nitrogen atmosphere, get part 2-(2'-phenacyl)-pyridine (1.88g, 9.56mmol) in the reaction flask being dried, under room temperature, in part, add appropriate normal hexane, fully stirring and dissolving.Getting trimethyl aluminium 4.78mL (1M, 4.78mmol) is dissolved in appropriate normal hexane solvent.At 0 ℃, the hexane solution of part is slowly added drop-wise in trimethyl aluminium solution, there is precipitation, ice bath returns to stirring at room reaction 3h after half an hour, obtain yellow turbid liquid, standing and reacting spend the night after upper strata for approaching colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow metal A l title complex.1H NMR (CDCl3, TMS, 300MHz): δ (ppm)=-0.76 (s, 3H ,-CH3of metal), 6.17 (s, 1H ,-CH-), 7.11-8.86 (m, 9H, benzenH and pyridineH). specifically see Fig. 5.
Embodiment 6: the preparation of enol form pyridine metal Mg title complex
Under nitrogen atmosphere, get part 2-(2'-phenacyl)-pyridine (0.48g, 2.52mmol) in the reaction flask being dried, in part, add the abundant stirring and dissolving of appropriate normal hexane solvent, dibutylmagnesium 2.52mL (0.5M, 1.26mmol) is dissolved in appropriate normal hexane solvent.At 0 ℃, the hexane solution of part is slowly added drop-wise in zinc ethyl solution, there is immediately precipitation, ice bath returns to stirring at room reaction 3h after half an hour, obtain yellow turbid liquid, standing and reacting spend the night after upper strata for approaching colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow metal M g title complex.1HNMR(CDCl3,TMS,300MHz):δ(ppm)＝5.93(s,1H,-CH-),7.07-7.93(m,9H,benzenH?and?pyridineH)。
Embodiment 7: enol form pyridine metal Al title complex in ε-hexamethylene lactone ring opening polymerization reaction as the application of catalyzer
Under nitrogen protection; add the Al title complex 20 μ mol that are dissolved in the preparation in example 5 in toluene; ε-CL monomer 4mmol; the toluene solution that adds 20 μ mol Virahols; monomer: promotor: catalyzer=200:1:1; add tetrahydrofuran solvent to make solvent cumulative volume remain on 10mL, under agitation controlling temperature is 50 ℃, after reaction 2h; add 1mL Glacial acetic acid termination reaction; then add industrial alcohol 100mL, making product sedimentation is white polymer, suction filtration; clean; vacuum-drying 12h under normal temperature, the 0.85g polymkeric substance of weighing to obtain, yield is 93%.
Embodiment 8: enol form pyridine metal Mg title complex is being applied under nitrogen protection as catalyzer in the reaction of ε-hexamethylene lactone ring opening polymerization, add the Mg title complex 20 μ mol that are dissolved in the preparation in example 6 in toluene, ε-CL monomer 4mmol, the toluene solution that adds 20 μ mol Virahols, monomer: promotor: catalyzer=200:1:1, add tetrahydrofuran solvent to make solvent cumulative volume remain on 10mL, under agitation controlling temperature is 50 ℃, after reaction 30min, add 1mL Glacial acetic acid termination reaction, then add industrial alcohol 100mL, making product sedimentation is white polymer, suction filtration, clean, vacuum-drying 12h under normal temperature, the 0.33g polymkeric substance of weighing to obtain, yield is 36%.
Claims (5)
1. a 1:2 type enol form pyridinium metal complex, is characterized in that, structural formula is:
Wherein: R
1=H, CH
3; R
2=CH
3, Ar, Bu
t;
M=Mg, R '=Bu, n=2 or M=Zn, R '=Et, n=2 or M=Al, R '=Me, n=3.
2. a kind of synthetic method of 1:2 type enol form pyridinium metal complex as claimed in claim 1, is characterized in that, comprises the steps:
(1) in anhydrous and oxygen-free condition, under ice bath, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-alkyl pyridine, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 ℃, the nitrile with 2-alkyl pyridine equimolar amount is dropwise added in reaction solution, react after half an hour, recover room temperature and continue reaction approximately 2 days, obtain brown solution;
At 0 ℃, in above-mentioned solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath stir about 1 day, add saturated NaOH to neutralize, until pH value is 7-8, add distilled water to solution to clarify; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removes methylene dichloride, in the underpressure distillation of 5mmHg pressure, collects cut, obtains enol form pyridine ligand;
(2) the enol form pyridine ligand and the MR ' that by mol ratio, are 2:1
nbe dissolved in respectively in normal hexane solvent, at 0 ℃, the hexane solution of enol form pyridine ligand dropwise added to MR '
nhexane solution in, the reaction deicing of dropping back half an hour is bathed, and rises to gradually room temperature and continues at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, adds normal hexane washing precipitation, standing, remove by filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
3. a 1:2 type enol form pyridinium metal complex, is characterized in that, its structural formula is:
Wherein: R
1=Ph; R
2=CH
3, Ar, Bu
t;
M=Mg, R '=Bu, n=2 or M=Zn, R '=Et, n=2 or M=Al, R '=Me, n=3.
4. a kind of synthetic method of 1:2 type enol form pyridinium metal complex as claimed in claim 3, is characterized in that, comprises the steps:
(1) in anhydrous and oxygen-free condition, under ice bath, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-benzyl-pyridine, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 ℃, the nitrile with 2-benzyl-pyridine equimolar amount is dropwise added in reaction solution, react after half an hour, recover room temperature and continue reaction approximately 2 days, obtain brown solution;
At 0 ℃, in above-mentioned solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath stir about 1 day, add saturated NaOH to neutralize, until pH value is 7-8, add distilled water to solution to clarify; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removes methylene dichloride, in the underpressure distillation of 5mmHg pressure, collects cut, obtains enol form pyridine ligand;
(3) the enol form pyridine ligand and the MR ' that by mol ratio, are 2:1
nbe dissolved in respectively in normal hexane solvent, at 0 ℃, the hexane solution of enol form pyridine ligand dropwise added to MR '
nhexane solution in, the reaction deicing of dropping back half an hour is bathed, and rises to gradually room temperature and continues at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, adds normal hexane washing precipitation, standing, remove by filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
Enol form pyridinium metal complex as described in claim 1 or 3 in polymerization ε-CL reaction as the application of catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410262368.5A CN104017004B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410262368.5A CN104017004B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104017004A true CN104017004A (en) | 2014-09-03 |
| CN104017004B CN104017004B (en) | 2016-02-10 |
Family
ID=51434049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410262368.5A Expired - Fee Related CN104017004B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104017004B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968036A (en) * | 2016-03-25 | 2016-09-28 | 安徽红太阳新材料有限公司 | Metal complex for catalysis of caprolactone polymerization |
| CN106928266A (en) * | 2017-03-03 | 2017-07-07 | 山西大学 | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
| CN107417716A (en) * | 2017-06-09 | 2017-12-01 | 山西大学 | A kind of enol form pyrazine metal complex and synthetic method and application |
| CN111363127A (en) * | 2020-04-02 | 2020-07-03 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085788A (en) * | 2007-07-09 | 2007-12-12 | 山西大学 | Metal complex using pyridine as matrix and synthetic method thereof |
-
2014
- 2014-06-12 CN CN201410262368.5A patent/CN104017004B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085788A (en) * | 2007-07-09 | 2007-12-12 | 山西大学 | Metal complex using pyridine as matrix and synthetic method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHENG ZHANG ET AL.: ""N,O-chelate aluminum and zinc complexes:synthesis and catalysis in the ring-opening polymerization ofε-caprolactone"", 《APPL. ORGANOMETAL. CHEM.》 * |
| MARKUS GRASER ET AL.: ""Structurally diverse pyridyl or quinolyl enolato/enamido metal complexes of Li, Zr, Fe, Co, Ni, Cu and Zn"", 《INORGANICA CHIMICA ACTA》 * |
| MARKUS GRASER ET AL.: ""Structurally diverse pyridyl or quinolyl enolato/enamido metal complexes of Li, Zr, Fe, Co, Ni, Cu and Zn"", 《INORGANICA CHIMICA ACTA》, vol. 401, 26 March 2013 (2013-03-26), XP028534580, DOI: doi:10.1016/j.ica.2013.02.040 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968036A (en) * | 2016-03-25 | 2016-09-28 | 安徽红太阳新材料有限公司 | Metal complex for catalysis of caprolactone polymerization |
| CN106928266A (en) * | 2017-03-03 | 2017-07-07 | 山西大学 | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
| CN107417716A (en) * | 2017-06-09 | 2017-12-01 | 山西大学 | A kind of enol form pyrazine metal complex and synthetic method and application |
| CN111363127A (en) * | 2020-04-02 | 2020-07-03 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
| CN111363127B (en) * | 2020-04-02 | 2021-05-14 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104017004B (en) | 2016-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Romain et al. | NHC bis-phenolate aluminum chelates: synthesis, structure, and use in lactide and trimethylene carbonate polymerization | |
| CN104017004A (en) | 1:2 type enol-form pyridine metal complexes and preparation method and application thereof | |
| JP5214609B2 (en) | Recovery of bis (diarylphenol) ligands during the production of isopulegol | |
| CZ278978B6 (en) | Diethers used in the preparation of ziegler-natt catalysts | |
| US20210163514A1 (en) | Compound of 3,3,3',3'-tetramethyl-1,1'-spirobiindane-based phosphine ligand, and preparation method thereof | |
| Chen et al. | Synthesis of a C2-symmetric chiral bipyridyldiol ligand and its application in the enantioselective addition of diethylzinc to substituted benzaldehydes | |
| CN109096318B (en) | Method for preparing organic boron compound and beta-hydroxy compound under catalysis of copper ion-loaded Y-type molecular sieve | |
| CN104031075B (en) | A kind of 1:1 type enol form quinoline metal complex and synthetic method thereof and application | |
| CN102180862B (en) | Method for preparing (4R-cis)-6-substituted-2,2-dimethyl-1,3-dioxane-4-tert-butyl acetate | |
| CN104017005B (en) | A kind of 1:1 type enol form pyridinium metal complex and its preparation method and application | |
| Singer et al. | Synthesis of a tridentate ligand for use in TiIV‐catalyzed acetate aldol addition reactions | |
| KR20140029373A (en) | N-heterocyclic carbene based zirconium complexes for use in lactones ring opening polymerization | |
| CN104031079B (en) | A kind of 1:2 type enol form aluminum quinoline complexes and synthetic method thereof and application | |
| CN104231234B (en) | Amino-pyrroles zinc Li metal Catalysts and its preparation method and application | |
| Gonzalez-Lopez et al. | Enantioselective synthesis of (+)-gossonorol and related systems using organozinc reagents | |
| CN102643417B (en) | Preparation method and application of phenyl-bridged guanyl binuclear rare-earth metal catalyst | |
| CN110483503B (en) | Imidazole carbene ligand with amide remote basic functional group and synthesis method and application thereof | |
| CN107417716B (en) | A kind of enol form pyrazine metal complex and synthetic method and application | |
| CN102260283B (en) | Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof | |
| CN101880210B (en) | Preparation method for conjugated diene compound | |
| KR102366890B1 (en) | Method for producing iron complex and method for producing ester compound using iron complex | |
| CN109053569B (en) | Method for synthesizing 8-hydroxyquinoline | |
| CN108503812B (en) | Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing o-phenylenediamine group | |
| CN106928266B (en) | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application | |
| CN101544672B (en) | Organic antimony compound bearing a nitrogen-bridged ligand and its preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160210 Termination date: 20180612 |