CN104031075A - 1:1 type enol quinoline metal complexes as well as synthetic method and application thereof - Google Patents
1:1 type enol quinoline metal complexes as well as synthetic method and application thereof Download PDFInfo
- Publication number
- CN104031075A CN104031075A CN201410262403.3A CN201410262403A CN104031075A CN 104031075 A CN104031075 A CN 104031075A CN 201410262403 A CN201410262403 A CN 201410262403A CN 104031075 A CN104031075 A CN 104031075A
- Authority
- CN
- China
- Prior art keywords
- solution
- metal complexes
- reaction
- enol form
- add
- 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
Abstract
The invention provides 1:1 type enol quinoline metal complexes as well as a synthetic method and application thereof. The method is characterized by using an enol quinoline coordinated ligand as a transfer reagent to react with alkylating reagents of magnesium, aluminium and zinc to synthesize a series of metal complexes. Such kind of [N,O] bidentate metal complexes can be used for catalyzing ring opening polymerization of aliphatic lactones. The method for synthesizing the complexes is simple, is lower in condition requirements and is higher in yield. The synthesized complexes have good catalytic activities and higher selectivity in ring opening polymerization of lactones. Such kind of complexes can be used for catalytically synthesizing 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.
Background technology
Polyester has broad application prospects as a kind of type material, be subject to extensive concern by ring-opening polymerization (ROP) synthesizing polyester, how to find the catalyzer that catalytic activity is high, controllability is good to become the difficult point of capturing, whether environmental protection also more and more comes into one's own catalyzer simultaneously.In the past few decades, polyester, particularly poly-hexamethylene lactone (PCL), polylactide (PLA), have attracting especially premium properties: the one, synthesize its monomer, for example ε-CL, LA is renewable resources, and polymkeric substance is from be easy to resolve into nontoxic material in environment or organism; The 2nd, as rac-Lactide, have the monomer of two chiral centres, the catalyzer of through performance excellence, can obtain having the polymkeric substance of different stereo microstructures, this creates a difference their crystal formation and degradation rate, and then affects the performances such as their intensity, thermostability, degradation speed.
Although polyester can obtain by polycondensation, polyester ring-opening polymerization causes by metal catalyst, carries out according to coordination-insertion mechanism, can obtain molecular weight controllability better, the polymkeric substance of composition rule.So far, a series of metal catalyst has obtained extensive and deep research, comprises potassium, lithium, magnesium, zinc, iron, calcium, aluminium, tin, yttrium, lanthanide series metal etc.But catalyst content is higher in the polymkeric substance generally obtaining, some metal also has toxicity.Zinc and magnesium are nontoxic for life entity, and particularly magnesium has very high catalytic activity simultaneously, thereby it has obtained investigator's extensive concern.
Summary of the invention
The monokaryon zinc, magnesium complex and the synthetic method thereof that the object of the present invention is to provide a kind of 1:1 type enol form chinoline coordination, this metal complexes can be used as the catalyzer of cyclic esters ring-opening polymerization.
A kind of 1:1 type enol form quinoline metal complexes provided by the invention, its structural formula is:
Wherein: M is zinc or magnesium, in the time that M is zinc, R is ethyl, and in the time that M is magnesium, R is butyl; R
1for methyl, the tertiary butyl, phenyl, O-methoxy or to methoxyl group;
The synthetic method of a kind of 1:1 type enol form quinoline metal complexes provided by the invention, comprises the steps:
(1) under condition of ice bath, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-toluquinoline, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, will dropwise add in reaction solution with the nitrile of 2-toluquinoline equimolar amount, react after half an hour, reply room temperature and continue reaction 2 days, stop stirring, obtain solution;
At 0 DEG C, in solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath and stirs 1 day, obtain yellow solution, add saturated NaOH to neutralize, until PH=8; With dichloromethane extraction three times, add anhydrous magnesium sulfate drying 1 day, be spin-dried for solvent, adding volume ratio is methylene dichloride and the normal hexane recrystallization of 1:1, separates out and obtains enol form quinoline part;
(2) the enol form quinoline part that is 1:1 by mol ratio and zinc ethyl or dibutylmagnesium are dissolved in respectively in normal hexane solvent, at 0 DEG C, the hexane solution of part is dropwise added in the hexane solution of zinc ethyl or dibutylmagnesium, reacting the deicing of dropping back half an hour bathes, rise to gradually room temperature, continue at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, add normal hexane washing precipitation, leave standstill, remove by filter filtrate, precipitation obtains 1:1 type enol form quinoline metal complexes through condensing crystal.
1:1 type enol form quinoline magnesium prepared by the present invention, zinc metal complexes, as catalyzer, are used in conjunction with initiator benzylalcohol or Virahol, react for ε-hexamethylene lactone ring opening polymerization.
Compared with prior art, advantage of the present invention:
The present invention, by changing substituting group, obtains having the part of different spaces steric hindrance and electronic effect, forms title complex with different metal effect, preparation method is simple, conditional request is relatively low, and productive rate is relatively high, and the title complex obtaining is used for catalysis ring-opening polymerization.The advantages such as it is little that such catalyzer has toxicity, and biocompatibility is good and catalytic activity is high, and polymer architecture is controlled are a kind of development prospect lactone ring opening polymerization catalyzer widely.
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-(2-quinolyl) methyl phenyl ketone
Under nitrogen atmosphere, 2-toluquinoline (29.14mmol, 3.94ml) is added in reaction flask, then add 100mL tetrahydrofuran (THF) fully to stir and make its dissolving.Under condition of ice bath, dropwise slowly add the n-Butyl Lithium (58.28mmol, 23.13mL) of two times of equivalents, the color of solution becomes scarlet, and ice bath returns to room temperature and continues to stir 3h after half an hour;
Under condition of ice bath, get cyanophenyl (29.14mmol, 2.98ml) and be slowly added drop-wise in above-mentioned reaction solution, solution becomes the Powdered thing of muddy adularescent and occurs.Reaction returns to room temperature, stirring reaction 2 days after half an hour.Under condition of ice bath, 60% the vitriol oil is joined in reaction solution to pH=1, continue to stir 1 day.Add saturated KOH neutralization reaction liquid to pH=7~8, use dichloromethane extraction three times, obtain scarlet clear solution, add appropriate anhydrous magnesium sulfate drying 1 day, be spin-dried for solvent, obtain garnet caking thing.Add normal hexane: methylene dichloride=1:1 recrystallization, separate out and obtain orange red solid, 4.078g, productive rate 56.7%.
1H?NMR(400MHz,DMSO)δ=6.26(s,1H),7.05(d,J=9.1Hz,1H),7.25(t,J=7.3Hz,1H),7.36-7.42(m,3H),7.53(t,J=7.6Hz,1H),7.60(d,J=8.2Hz,1H),7.64(d,J=7.8Hz,1H),7.83-7.92(m,3H),15.57(s,1H)。
Embodiment 2: with the preparation of the lactone ring opening polymerization catalyzer of Metal Zn coordination
Weigh 2-(2-quinolyl) methyl phenyl ketone (0.749g, 3mmol), join in reaction flask, in this bottle, add the hexane solution that 15mL is dry.Prepare again a standard jar, first add the hexane solution that 10mL is dry, then extract 3mL zinc ethyl (1mol/L) and join in standard jar.Under condition of ice bath, the hexane solution of part 2-(2-quinolyl) methyl phenyl ketone is slowly splashed in zinc ethyl solution, there are a large amount of precipitations to produce, react the deicing of dropping back half an hour and bathe, rise to gradually room temperature, continue stirring reaction 3h, sufficient standing, suction filtration falls upper solution, then adds the washing of 10mL normal hexane, filter and drain, finally obtain metallic zinc title complex.
1H?NMR(600MHz,CDCl
3)δ=0.86(s,4H),1.25(t,J=7.0Hz,6H),6.22(s,2H),7.19(dd,J=5.4,8.1Hz,2H),7.26(s,6H),7.40-7.31(m,4H),7.56(dd,J=8.1,20.5Hz,4H),7.88(d,J=8.9Hz,2H),7.97(dd,J=6.5,3.0Hz,4H)。
Embodiment 3: with the preparation of the lactone ring opening polymerization catalyzer of metal M g coordination
Weigh 2-(2-quinolyl) methyl phenyl ketone (0.749g, 3mmol), join in reaction flask, in this bottle, add the hexane solution that 15mL is dry.Prepare again a standard jar, first add the hexane solution that 10mL is dry, then extract 6mL dibutylmagnesium (0.5mol/L) and join in standard jar.Under condition of ice bath, the hexane solution of part 2-(2-quinolyl) methyl phenyl ketone is slowly splashed in dibutylmagnesium solution, reacting the deicing of dropping back half an hour bathes, rise to gradually room temperature, continue stirring reaction 3h, sufficient standing, suction filtration falls upper solution, add again the washing of 10mL normal hexane, filter and drain, obtain Magnesium Complex.
1H?NMR(600MHz,CDCl
3)δ=0.79-0.95(m,4H)1.00(t,J=7.5Hz,4H),1.28(dd,J=5.4,8.7Hz,10H),6.09(s,2H),6.88(d,J=9.0Hz,2H),7.26(s,6H),7.44(s,4H),7.54(s,4H),7.67(d,J=8.9Hz,2H),7.95(s,4H)。
Embodiment 4: with ring-opening polymerization catalyst catalysis ε-hexamethylene lactone ring opening polymerization of Metal Zn coordination
Under nitrogen protection, add 10mL tetrahydrofuran solution to reaction flask, then add the Zn complex 20 μ mol of preparation in embodiment 2, then add the tetrahydrofuran solution of 20 μ mol promotor Virahols, stir 15min.Subsequently, add appropriate tetrahydrofuran solvent to make overall solution volume remain on 10mL left and right.Accurately add 8mmol 6-caprolactone monomer solution, keep monomer: catalyzer: promotor=400:1:1, stirs lower control temperature at 55 DEG C.After reaction 4h, add appropriate glacial acetic acid termination reaction, then add a large amount of industrial alcohols that product is separated out and obtain white polymer, filter supernatant liquid, then add the abundant washing and precipitating of appropriate ethanol, filtration drying, the 0.974g that weighs, yield 91.09%.
Embodiment 5: with ring-opening polymerization catalyst catalysis ε-hexamethylene lactone ring opening polymerization of metal M g coordination
Under nitrogen protection, add 10mL tetrahydrofuran solution to reaction flask, then add the Zn complex 20 μ mol of preparation in embodiment 3, then add the tetrahydrofuran solution of 20 μ mol promotor Virahols, stir 15min.Subsequently, add appropriate tetrahydrofuran solvent to make overall solution volume remain on 10mL left and right.Accurately add 8mmol 6-caprolactone monomer solution, keep monomer: catalyzer: promotor=400:1:1, stirs lower control temperature at 55 DEG C.After reaction 4h, add appropriate glacial acetic acid termination reaction, then add a large amount of industrial alcohols that product is separated out and obtain white polymer, filter supernatant liquid, then add the abundant washing and precipitating of appropriate ethanol, filtration drying, the 1.068g that weighs, yield 99.85%.
Claims (3)
1. a 1:1 type enol form quinoline metal complexes, is characterized in that, structural formula is:
Wherein: M is zinc or magnesium, in the time that M is zinc, R is ethyl; In the time that M is magnesium, R is butyl; R
1for methyl, the tertiary butyl, phenyl, O-methoxy or to methoxyl group.
2. the synthetic method of a kind of 1:1 type enol form quinoline metal complexes as claimed in claim 1, is characterized in that, comprises the steps:
(1) in anhydrous and oxygen-free condition, under low temperature, the n-Butyl Lithium of 2 molar equivalents dropwise to be stirred in the THF solution that adds 2-toluquinoline, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, will dropwise add in reaction solution with the nitrile of 2-toluquinoline equimolar amount, react after half an hour, reply room temperature and continue reaction 2 days, stop stirring, obtain red solution;
At 0 DEG C, in solution, dropwise add 60% vitriol oil to be hydrolyzed, until PH=1 removes ice bath and stirs 1 day, add saturated NaOH to neutralize, until PH=8; With dichloromethane extraction three times, with anhydrous magnesium sulfate drying 1 day, be spin-dried for solvent, adding volume ratio is methylene dichloride and the normal hexane recrystallization of 1:1, obtains enol form quinoline part;
(2) the enol form quinoline part that is 1:1 by mol ratio and zinc ethyl or dibutylmagnesium are dissolved in respectively in normal hexane solvent, at 0 DEG C, the hexane solution of enol form quinoline part is dropwise joined in the hexane solution of zinc ethyl or dibutylmagnesium, reacting the deicing of dropping back half an hour bathes, rise to gradually room temperature and continue at least 3h of stirring reaction, sufficient standing, suction filtration falls upper solution, add normal hexane washing precipitation, leave standstill, remove by filter filtrate, precipitation process, condensing crystal obtains 1:1 type enol form quinoline metal complexes.
Enol form quinoline metal complexes as claimed in claim 1 in polymerization ε-CL reaction as the application of catalyzer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410262403.3A CN104031075B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:1 type enol form quinoline metal complex and synthetic method thereof and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410262403.3A CN104031075B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:1 type enol form quinoline metal complex and synthetic method thereof and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104031075A true CN104031075A (en) | 2014-09-10 |
CN104031075B CN104031075B (en) | 2016-03-30 |
Family
ID=51462094
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410262403.3A Expired - Fee Related CN104031075B (en) | 2014-06-12 | 2014-06-12 | A kind of 1:1 type enol form quinoline metal complex and synthetic method thereof and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104031075B (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 |
CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
CN115160302A (en) * | 2022-07-25 | 2022-10-11 | 万华化学集团股份有限公司 | Isoquinoline-oxazoline metalloid organic catalyst and preparation method and application thereof |
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 CN201410262403.3A patent/CN104031075B/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 (2)
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》 * |
Cited By (7)
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 |
CN106928266B (en) * | 2017-03-03 | 2019-02-26 | 山西大学 | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
CN109456342B (en) * | 2018-11-23 | 2020-12-25 | 山西大学 | 1, 2-addition quinolyl lithium complex and synthesis method and application thereof |
CN115160302A (en) * | 2022-07-25 | 2022-10-11 | 万华化学集团股份有限公司 | Isoquinoline-oxazoline metalloid organic catalyst and preparation method and application thereof |
CN115160302B (en) * | 2022-07-25 | 2024-02-27 | 万华化学集团股份有限公司 | Isoquinoline-oxazoline metal organic catalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104031075B (en) | 2016-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104031075B (en) | A kind of 1:1 type enol form quinoline metal complex and synthetic method thereof and application | |
CN104031079B (en) | A kind of 1:2 type enol form aluminum quinoline complexes and synthetic method thereof and application | |
CN103864659B (en) | Chiral imines phenol oxygen base zinc, magnesium compound and its preparation method and application | |
CN108129515A (en) | A kind of synthetic method of bis-phosphite | |
CN104017004B (en) | A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application | |
Bakthavachalam et al. | N-Benzoylbenzamidinate complexes of aluminium: highly efficient initiators for the ring-opening polymerization of ε-caprolactone | |
CN109320555A (en) | A kind of synthetic method of bis-phosphite | |
Yildiz et al. | Preparation of single-site tin (IV) compounds and their use in the polymerization of ε-caprolactone | |
CN104231234A (en) | Aminopyrrole zinc-lithium bimetallic catalyst, preparation method and application thereof | |
CN105294436A (en) | Method for synthesizing monomenthyl succinate | |
CN104017005B (en) | A kind of 1:1 type enol form pyridinium metal complex and its preparation method and application | |
CN102827169B (en) | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand | |
JP2018516886A (en) | Carboxylic ion cross-linked dinuclear iron sulfur cluster fluorescent probe, its production method and its use | |
CN107417716B (en) | A kind of enol form pyrazine metal complex and synthetic method and application | |
CN104327284A (en) | Preparation method of supramolecular hydrogel | |
CN102260283B (en) | Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof | |
CN104926707B (en) | A kind of synthetic method of pharmaceutical intermediate | |
CN106008946B (en) | A kind of preparation method of N-heterocyclic carbine metal aluminium compound and application | |
CN102838637A (en) | Imine phenol oxymagnesium compound, and preparation method and application thereof | |
CN106496579A (en) | Double structure primitive phthalic acid manganese polymer and preparation method thereof | |
CN106928266B (en) | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application | |
CN112707934A (en) | Alendronate calcium complex and preparation method thereof | |
CN102199167B (en) | Pyrrolidyl amino bidentate ligand aluminum complex and preparation method and application thereof | |
CN112724175A (en) | Minodronic acid calcium complex and preparation method thereof | |
RU2591197C1 (en) | Method for synthesis of heterothreenuclear coordination compound based on iminodiacetic acid salicylidenhydrazone |
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: 20160330 Termination date: 20180612 |