CN104017004B - A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application - Google Patents
A kind of 1:2 type enol form pyridinium metal complex and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of synthetic method and application of 1:2 type enol form pyridinium metal complex.The method is with the part of enol form pyridine coordination, and with this part for transfering reagent, a series of metal complexess synthesized with the alkylating reagent effect of magnesium, aluminium, zinc, this kind of enol form pyridinium metal complex can be used for the ring-opening polymerization of catalyze fatty race lactone.The method of title complex synthesis of the present invention is simple, and conditional request is lower, and productive rate is higher; The title complex of synthesis has good catalytic activity and comparatively highly selective to lactone ring opening polymerization.Because the good biocompatibility of this kind of catalyzer, toxicity are little, therefore, can perform well in catalyzing and synthesizing biodegradable polyester material.
Description
Technical field
The present invention relates to catalyst preparation technical field, be specifically related to the mononuclear title complex and preparation method thereof of a class [N, O] bitooth ligand and aluminium, magnesium and zinc coordination, 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 is except having high molecular feature, also has good biocompatibility and avirulent advantage, has become the focus of Material Field research.At present, the ring-opening polymerization of cyclic ester and lactide has more advantages relative to polycondensation, and as mild condition, monomer conversion is high, the high molecular that is easy to get and the narrow polymkeric substance etc. of molecular weight, and becomes and study the most deep method 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 research of tetraphenylporphyrin aluminium alkyl oxide to cyclic ester monomer ring-opening polymerization of the eighties report was comparatively early attempting of controlled catalytic ring-opening polymerization, the polyester that this catalyst system catalysis is formed has molecular weight can be predicted, the feature of narrow molecular weight distribution.In addition, Schiff class is similar to porphyrin and has the simple and advantage that part Scalability is strong of synthesis, and is widely studied.2005, NobuyoshiNomura study group reported a series of salicylyl imines class aluminum compound, can the ε of catalysis quickly and efficiently-hexamethylene lactone ring opening polymerization.Some aluminum alkoxide catalyzer are also had to study more recently.
Zinc-magnesium series catalysts
The metallic zinc title complex of N, O coordination studies the simple part of a class comparatively early, is also study a more class part.The people such as Tolman in 2003 report class amido phenols Zn (II) complex compound, and such catalyzer can cause the controlled ring-opening polymerization of rac-Lactide fast, can obtain the high and polymerization product of narrowly distributing of molecular weight.The metallic zinc compound of Salen type N, O coordination studies a widest class in cyclic esters ring-opening polymerization catalysis zinc system, and it can the rac-Lactide of catalysis efficiently Jian cyclopolymerization, and embody the feature of living polymerization.2010, the people such as Hayes obtained cationic Zn complex, can be polymerized by catalysis rac-lactide efficiently, and resulting polymers also had certain stereoselectivity.
Magnesium and zinc are all similar in a lot of attribute, but Mg is often seen as hard metal, Zn is then soft metal, and many organic ligands for stable Zn (II) can be formed stable with Mg (II) complexing and have the catalyzer of catalysis cyclic esters ring-opening polymerization activity too.Magnesium does not almost have toxicity concerning organism, and compared with aluminium, zinc catalyst, the activity of Mg catalyst is general higher, so carry out catalysis or cause cyclic esters ring-opening polymerization to be the focus that people study with magnesium complex always.
Magnesium, aluminium, zinc class catalyzer are the focus of research because its toxicity is little, and itself just may be used for catalyzed polymerization.Up to the present, find that catalysis LA ring-opening polymerization effect is it is preferred that zinc lactate, better can control the molecular weight of polymkeric substance, 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 a kind of magnesium of 1:2 type enol form pyridine coordination, zinc and aluminum complex and synthesis and this metal complexes thereof in aliphatic ester ring-opening polymerization as the application of catalyzer.
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, dropwise stirred by the n-Butyl Lithium of 2 molar equivalents and add in the THF solution of 2-alkyl pyridine under ice bath, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, the nitrile with 2-alkyl pyridine equimolar amount is dropwise added in reaction solution, after reacting half an hour, recover room temperature and continue reaction about 2 days, obtain brown solution;
At 0 DEG C, in above-mentioned solution, dropwise add 60% vitriol oil be hydrolyzed, until PH=1, remove ice bath and stir about 1 day, add saturated NaOH and neutralize, until pH value is 7-8, now produce white Na
2sO
4precipitation, adds distilled water and clarifies to solution; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, in the distillation of 5mmHg pressure, collect cut, obtain enol form pyridine ligand;
(2) by mol ratio be enol form pyridine ligand and the MR ' of 2:1
nbe dissolved in normal hexane solvent respectively, at 0 DEG C, the hexane solution of enol form pyridine ligand dropwise added MR '
nhexane solution in, reaction to be dropped back deicing bath half an hour, rises to room temperature gradually and continues stirring reaction at least 3h, sufficient standing, suction filtration falls upper solution, adds n-hexane precipitation, leaves standstill, cross and 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, dropwise stirred by the n-Butyl Lithium of 2 molar equivalents and add in the THF solution of 2-benzyl-pyridine under ice bath, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, the nitrile with 2-benzyl-pyridine equimolar amount is dropwise added in reaction solution, after reacting half an hour, recover room temperature and continue reaction about 2 days, obtain brown solution;
At 0 DEG C, in above-mentioned solution, dropwise add 60% vitriol oil be hydrolyzed, until PH=1, remove ice bath and stir about 1 day, add saturated NaOH and neutralize, until pH value is 7-8, now produce white Na
2sO
4precipitation, adds distilled water and clarifies to solution; In solution, add dichloromethane extraction three times, take off layer and add anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, in the distillation of 5mmHg pressure, collect cut, obtain enol form pyridine ligand;
(2) by mol ratio be enol form pyridine ligand and the MR ' of 2:1
nbe dissolved in normal hexane solvent respectively, at 0 DEG C, the hexane solution of enol form pyridine ligand dropwise added MR '
nhexane solution in, reaction to be dropped back deicing bath half an hour, rises to room temperature gradually and continues stirring reaction at least 3h, sufficient standing, suction filtration falls upper solution, adds n-hexane precipitation, leaves standstill, cross and filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
Enol form pyridine magnesium the present invention prepared, aluminium, zinc metal complexes can be used as catalyzer, with initiator benzylalcohol or Virahol with the use of, for ε-hexamethylene lactone ring opening polymerization reaction.
Compared with prior art, advantage of the present invention:
The present invention is by changing substituent R 1 and R2, obtain the part with different spaces steric hindrance and electronic effect, and then generate the title complex with different electronic effect and steric effect, preparation method is simple, conditional request is relatively low, and productive rate is relatively high, the title complex obtained be used for catalyzed ring opening polymerization reaction.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 carrying out under the dried high pure nitrogen of potassium post 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, adds the tetrahydrofuran (THF) of about 100mL drying, stir and make it fully dissolve.Under condition of ice bath, dropwise add n-Butyl Lithium 25.56mL (2.5M, 63.92mmol) with syringe, react deicing bath of dropping back half an hour and recover stirring at room temperature 3h, obtain dark red solution.
In nitrogen protection, get acetonitrile (1.66mL, 31.96mmol) with syringe under cryosel bath (-40 DEG C) condition and be dropwise added in previous step reaction flask, reaction recovers stirring at room temperature 2 days after half an hour, obtains brown solution.
Under condition of ice bath, the sulphuric acid soln adding 60% in reaction solution carries out acid hydrolysis, treats that pH reaches till 1, and react 1 day, solution colour becomes chocolate.Under condition of ice bath, add sulphuric acid soln in saturated sodium hydroxide He excessive, dissolve the solid of generation until solution clarification with a large amount of distilled water.Dichloromethane extraction is added three times in solution, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, distill at 5mmHg pressure, collect 75 DEG C of cuts (vacuum tightness is 0.85-0.90MPa), obtain glassy yellow oily matter 2-(4'-butanone base)-pyridine.Productive rate: 32.28%.1HNMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=2.11 (s, 3H,-CH3), 3.89 (s, 2H,-CH2), 7.26 (m, 2H, four, fivepositionofpyridine), 7.70 (m, 1H, threepositionofpyridine), 8.46 (d, J=3.9,1H, sixpositionofpyridine) .13CNMR ((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) of about 100mL drying, stir and make it fully dissolve.Under condition of ice bath, dropwise add n-Butyl Lithium 25.56mL (2.5M, 61.46mmol), react deicing bath of dropping back half an hour and recover stirring at room temperature 3h, obtain dark red solution.
Under nitrogen protection, cryosel bath (-40 DEG C) condition, get cyanophenyl (3.15mL, 30.73mmol) and be dropwise added in previous step reaction flask, ice bath reacts deicing bath of dropping back half an hour and recovers stirring at room temperature 2 days, obtains brown-red solution.
Be hydrolyzed under condition of ice bath reaction, adds the sulphuric acid soln (about 30mL) of a certain amount of 60%, treat that pH reaches till 1 in reaction flask, and react 1 day, solution colour becomes chocolate.Under condition of ice bath, add sulphuric acid soln in saturated sodium hydroxide He excessive, dissolve the solid of generation until solution clarification with a large amount of distilled water.Dichloromethane extraction is added three times in solution, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, in the distillation of 5mmHg pressure, collect 135 DEG C of cuts (vacuum tightness is 0.85-0.90MPa), obtain yellow oil product, yellow solid 2-(2'-phenacyl)-pyridine is become subsequently, productive rate: 30.73% because product is easy to solidification.1HNMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=4.54 (s, 1H,-CH), 6.37-8.47 (m, 9H, benzenandpyridine), 15.38 (s, 1H, N-Hofpyridine) .13CNMR ((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 (benzenCandpyridineC), 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, get 2-picoline (2.89g, 31.08mmol) be injected in 250mL reaction flask with syringe, the tetrahydrofuran (THF) adding 100mL drying makes it fully dissolve.Under condition of ice bath, dropwise add n-Butyl Lithium 24.86mL (2.5M, 62.17mmol), react deicing bath of dropping back half an hour and recover stirring at room temperature 3h, obtain dark red solution.
In nitrogen protection; with getting o-methyl-benzene nitrile (3.68mL under cryosel bath (-40 DEG C) condition; 31.08mmol) and be dropwise added in previous step reaction flask, ice bath reaction deicing bath of dropping back half an hour recovers stirring at room temperature 2 days, obtains dark red solution.
Be hydrolyzed under condition of ice bath reaction, adds the sulphuric acid soln of 60% in reaction flask, all precipitations all dissolved and pH value reaches 1.Remove ice bath room temperature reaction 1 day, obtain dark solution.Slowly saturated sodium hydroxide solution neutralisation of sulphuric acid is dripped under ice bath, add distilled water dissolution precipitation subsequently to clarify to solution, dichloromethane extraction is added three times in solution, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, distills at 5mmHg pressure, collect 138 ° of C cuts (vacuum tightness is 0.85-0.90MPa), obtain yellowish red color oily matter.Subsequently, cross post and purify further (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%.1HNMR ((CD3) 2SO, TMS, 300MHz): δ (ppm)=2.40 (s, 3H ,-CH3ofbenzen), 7.11-8.49 (m, 8H, Hofbenzenandpyridine), 15.25-15.38 (s, 1H, N-Hofpyridine) .13CNMR ((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 (benzenCandpyridineC), 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 dried reaction flask, appropriate normal hexane solvent is added in part, abundant stirring and dissolving, get zinc ethyl 1.28mL (1M, 1.28mmol) to be again dissolved in appropriate normal hexane solvent.At 0 DEG C, the hexane solution of part is slowly added drop-wise in zinc ethyl solution, there is precipitation immediately, ice bath returns to stirring at room temperature reaction 3h after half an hour, obtain deep yellow color cloud liquid, standing and reacting spend the night after upper strata for close to colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow metal Zn title complex (4).1HNMR (CDCl3, TMS, 300MHz): δ (ppm)=5.921 (s, 1H ,-CH-), 6.782-7.052 (m, 9H, benzenHandpyridineH), 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 dried reaction flask, in part, add appropriate normal hexane under room temperature, abundant stirring and dissolving.Get trimethyl aluminium 4.78mL (1M, 4.78mmol) to be dissolved in appropriate normal hexane solvent.At 0 DEG C, the hexane solution of part is slowly added drop-wise in trimethylaluminium solution, there is precipitation, ice bath returns to stirring at room temperature reaction 3h after half an hour, obtain yellow turbid liquid, standing and reacting spend the night after upper strata for close to colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow metal Al title complex.1HNMR (CDCl3, TMS, 300MHz): δ (ppm)=-0.76 (s, 3H,-CH3ofmetal), 6.17 (s, 1H ,-CH-), 7.11-8.86 (m, 9H, benzenHandpyridineH). 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 dried reaction flask, the abundant stirring and dissolving of appropriate normal hexane solvent is added in part, dibutylmagnesium 2.52mL (0.5M, 1.26mmol) is dissolved in appropriate normal hexane solvent.At 0 DEG C, the hexane solution of part is slowly added drop-wise in zinc ethyl solution, there is precipitation immediately, ice bath returns to stirring at room temperature reaction 3h after half an hour, obtain yellow turbid liquid, standing and reacting spend the night after upper strata for close to colourless solution, lower floor is yellow solid, filters out supernatant liquid, and solvent removed in vacuo obtains yellow metal Mg title complex.1HNMR(CDCl3,TMS,300MHz):δ(ppm)＝5.93(s,1H,-CH-),7.07-7.93(m,9H,benzenHandpyridineH)。
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 be dissolved in toluene by example 5 preparation Al title complex 20 μm of ol; ε-CL monomer 4mmol; add the toluene solution of 20 μm of ol Virahols; monomer: promotor: catalyzer=200:1:1; adding tetrahydrofuran solvent makes total solvent volume remain on 10mL, and under agitation control temperature is 50 DEG C, after reaction 2h; add 1mL Glacial acetic acid termination reaction; then add industrial alcohol 100mL, make product sedimentation be white polymer, suction filtration; cleaning; vacuum-drying 12h under normal temperature, 0.85g polymkeric substance of weighing to obtain, yield is 93%.
Embodiment 8: enol form pyridine metal Mg title complex in ε-hexamethylene lactone ring opening polymerization reaction as the application of catalyzer under nitrogen protection, add be dissolved in toluene by example 6 preparation Mg title complex 20 μm of ol, ε-CL monomer 4mmol, add the toluene solution of 20 μm of ol Virahols, monomer: promotor: catalyzer=200:1:1, adding tetrahydrofuran solvent makes total solvent volume remain on 10mL, under agitation control temperature is 50 DEG C, after reaction 30min, add 1mL Glacial acetic acid termination reaction, then industrial alcohol 100mL is added, product sedimentation is made to be white polymer, suction filtration, cleaning, vacuum-drying 12h under normal temperature, to weigh to obtain 0.33g polymkeric substance, yield is 36%.
Claims (3)
1. a 1:2 type enol form pyridinium metal complex, is characterized in that, its structural formula is:
And prepared by following steps:
(1) in anhydrous and oxygen-free condition, dropwise stirred by the n-Butyl Lithium of 2 molar equivalents and add in the THF solution of 2-alkyl pyridine under ice bath, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, the nitrile with 2-alkyl pyridine equimolar amount is dropwise added in reaction solution, after reacting half an hour, recover room temperature and continue reaction 2 days, obtain brown solution;
At 0 DEG C, in above-mentioned solution, dropwise add 60% vitriol oil be hydrolyzed, until pH=1, remove ice bath and stir 1 day, adding saturated NaOH and neutralize, until pH value is 7-8, adds distilled water and clarify to solution; In solution, add dichloromethane extraction three times, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, in the distillation of 5mmHg pressure, collect cut, obtain enol form pyridine ligand;
(2) by mol ratio be enol form pyridine ligand and the MR ' of 2:1
nbe dissolved in normal hexane solvent respectively, at 0 DEG C, the hexane solution of enol form pyridine ligand dropwise added MR '
nhexane solution in, reaction to be dropped back deicing bath half an hour, rises to room temperature gradually and continues stirring reaction at least 3h, sufficient standing, suction filtration falls upper solution, adds n-hexane precipitation, leaves standstill, cross and filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
2. a 1:2 type enol form pyridinium metal complex, is characterized in that, its structural formula is:
And prepared by following steps:
(1) in anhydrous and oxygen-free condition, dropwise stirred by the n-Butyl Lithium of 2 molar equivalents and add in the THF solution of 2-benzyl-pyridine under ice bath, reaction returns to room temperature and continues reaction 3h after half an hour, obtain dark red solution;
At 0 DEG C, the nitrile with 2-benzyl-pyridine equimolar amount is dropwise added in reaction solution, after reacting half an hour, recover room temperature and continue reaction 2 days, obtain brown solution;
At 0 DEG C, in above-mentioned solution, dropwise add 60% vitriol oil be hydrolyzed, until pH=1, remove ice bath and stir 1 day, adding saturated NaOH and neutralize, until pH value is 7-8, adds distilled water and clarify to solution; In solution, add dichloromethane extraction three times, take off layer and add appropriate anhydrous magnesium sulfate drying 1 day, rotary evaporation, removing methylene dichloride, in the distillation of 5mmHg pressure, collect cut, obtain enol form pyridine ligand;
(3) by mol ratio be enol form pyridine ligand and the MR ' of 2:1
nbe dissolved in normal hexane solvent respectively, at 0 DEG C, the hexane solution of enol form pyridine ligand dropwise added MR '
nhexane solution in, reaction to be dropped back deicing bath half an hour, rises to room temperature gradually and continues stirring reaction at least 3h, sufficient standing, suction filtration falls upper solution, adds n-hexane precipitation, leaves standstill, cross and filter filtrate, precipitation is through concentrated, and crystallization obtains 1:2 type enol form pyridinium metal complex.
3. profit requires enol form pyridinium metal complex described in 1 or 2 in ε-hexamethylene lactone polymerization as the application of catalyzer.
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| "N,O-chelate aluminum and zinc complexes:synthesis and catalysis in the ring-opening polymerization ofε-caprolactone";Cheng Zhang et al.;《Appl. Organometal. Chem.》;20081010;第23卷;第11页右栏Scheme 2及第13页右栏最后一段 * |
| "Structurally diverse pyridyl or quinolyl enolato/enamido metal complexes of Li, Zr, Fe, Co, Ni, Cu and Zn";Markus Graser et al.;《Inorganica Chimica Acta》;20130326;第401卷;第42页Scheme 5，第46页左栏第2段及第48页右栏第三段 * |
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