CN102898481A - Synthesis method for late transition metal complex catalyst - Google Patents
Synthesis method for late transition metal complex catalyst Download PDFInfo
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- CN102898481A CN102898481A CN2012103256468A CN201210325646A CN102898481A CN 102898481 A CN102898481 A CN 102898481A CN 2012103256468 A CN2012103256468 A CN 2012103256468A CN 201210325646 A CN201210325646 A CN 201210325646A CN 102898481 A CN102898481 A CN 102898481A
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Abstract
The invention relates to a synthesis method for a late transition metal complex catalyst. The method comprises: mixing N,N-dimethyl formamide and water to obtain a N,N-dimethyl formamide and water mixed solution; sequentially adding benzyl chloride, sodium azide and 2-ethynylpyridine to obtain a reaction mixture solution; sequentially adding anhydrous sodium carbonate, ascorbic acid and copper sulfate to the reaction mixture solution, and carrying out a reaction for 20-24 hours at a room temperature under normal pressure; adding ethyl acetate to the reaction system, extracting an organic phase, adding distilled water to the organic phase to wash the organic phase, and carrying out drying by using anhydrous sodium sulfate; filtering to remove the anhydrous sodium sulfate; carrying out distilling to remove the ethyl acetate solvent to obtain a ligand compound adopting pyridine as a precursor; under nitrogen protection, adding a dichloromethane solution, the ligand compound and a late transition metal compound to a reactor; carrying out a reaction for 1.5-2 hours under nitrogen protection at a room temperature under normal pressure; standing; filtering and removing the supernatant; carrying out vacuum draining on the remaining solid; and adopting n-hexane to wash to obtain the late transition metal complex catalyst. The synthesis method has the following advantages that: the substituted group and the late transition metal compound can be flexibly changed, no sensitivity on oxygen and water is provided, a reaction process is simple, and yield is high.
Description
Technical field
The invention belongs to a kind of synthetic method, specifically the synthetic method of related a kind of late transition metal complex catalyst.
Background technology
" Click Chemistry "-" click chemistry ", it is a kind of novel method of synthesizing fast a large amount of compounds that the Americanized scholar Sharpless of calendar year 2001 Nobel chemistry Prize winner proposes, purport is the splicing by junior unit, finishes the chemosynthesis of varied molecule fast and reliablely." click chemistry " essence refers to select the raw material that is easy to get, by reliable, efficient and tool optionally chemical reaction realize that the carbon heteroatoms connects (C-X-C), the powerful and practical synthetic method of covers low-cost, fast synthetic a large amount of new compounds.Its core is to utilize a series of reliable, modular reactions to generate to contain heteroatomic compound.These reactions have following feature usually: (1) is raw materials used to be easy to get; (2) operation is simple, and mild condition is insensitive to oxygen, water; (3) product yield is high, selectivity is good; (4) the easy purifying of product, aftertreatment are simple.
The target of " click chemistry " and thought embody the most fully in the trinitride of on-catalytic and copper catalysis-alkynes cycloaddition reaction.The former is able to thorough in the sixties in 20th century to the research of the eighties Rolf Huisgen, and is asserted the important new reaction of a class.Calendar year 2001, the Meldal study group of Denmark and the Sharpless study group of the U.S. have independently found respectively catalysed reaction of copper, and this reaction needed adopts terminal alkyne, under the condition of gentleness, can obtain the 1,2,3-triazoles cyclocomplex of single Isosorbide-5-Nitrae-replacement.
Develop so far, " click chemistry " has been widely used in a plurality of fields of chemistry subject, comprises the fields such as polyreaction, medicament research and development, bio-science and materials chemistry.The stereoselectivity of such reaction aspect synthetic Isosorbide-5-Nitrae-triazole is better, and productive rate is higher.Wherein, " Click " reaction under cupreous compound catalysis especially obtains people's extensive concern, has good researching value." Click " reaction specifically applies to the organic field of metal, be embodied in the ligand compound that obtains by this reaction and the mating reaction of various metals compound, the compound of copper, rhenium, silver, gold for example, wherein the effect of the compound of rhenium and part has applied to the fields such as medical treatment, physics aspect.The cycloaddition of trinitride-alkynes is counter to be of great use a kind of and to prepare easily the method for 1,2,3-triazoles compound.In recent years, people are by conversion 1,2, substituted radical on the 3-triazole ring is studied the performance of the each side of this compounds, finds that the method is at preparation Isosorbide-5-Nitrae-disubstituted 1, the effect of 2,3-triazole compounds aspect is fine, and this just provides more wide space for studying from now on this compounds.
In sum, organic compound catalyzer take copper, rhenium, silver, gold, platinum is arranged in the technology mainly now as main, used metallic compound is the noble metal compound in the preparation of such catalyzer, and cost is higher.Through the document report, catalytic activity was all higher when the rear transition metal organic catalyst was used for ethylene polymerization, and the late transition metal complex catalyst take pyridine as parent among the present invention there is not yet report.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of late transition metal complex catalyst take pyridine as parent.
The present invention is based on " click chemistry " synthetic method, namely take trinitride and end position alkynes as raw material, and the cycloaddition reaction under copper catalysis (CuAAC), the present invention fits to a class bidentate orgnometallic catalyst.2-ethynyl pyridine, benzyl chloride, sodiumazide are reacted, subsequently the gained ligand metal is obtained a kind of pyridine and triazole by the orgnometallic catalyst of methylene-bridged.
Provide the late transition metal complex catalyst synthetic method take pyridine as parent may further comprise the steps among the present invention:
(1) presses DMF (DMF): H
2The mol ratio of O is 3.5～4:1; Optimum mole ratio is 4:1, with DMF and H
2O mixes, and obtains DMF and water mixed solution, and by benzyl chloride: sodiumazide: 2-ethynyl pyridine mol ratio is 1.1～1.2:1.1～1.2:1, at DMF and H
2In the mixing solutions of O, add successively benzyl chloride, sodiumazide, 2-ethynyl pyridine, obtain the solution of reaction mixture;
(2) by anhydrous sodium carbonate: xitix: the copper sulfate mol ratio is 2.4～2.5:2:1, adds successively anhydrous sodium carbonate, xitix, copper sulfate in the solution of reaction mixture, reacts at normal temperatures and pressures 20～24h;
(3) after the reaction, in reaction system, add ethyl acetate, extracted organic phase, in organic phase, add again the distilled water wash organic phase, and carry out drying with anhydrous sodium sulphate, after anhydrous sodium sulphate is filtered out, steam ethyl acetate solvent, namely obtain the ligand compound take pyridine as parent;
(4) under the nitrogen protection; in reactor, add dichloromethane solution; by ligand compound: the mol ratio of rear transition metal compound is 1:1～1.1; add ligand compound and rear transition metal compound; under nitrogen protection, normal temperature and pressure, react 1.5～2h, leave standstill, filter out supernatant liquid; remaining solid is drained under vacuum, again with obtaining late transition metal complex catalyst after the normal hexane washing.
Aforesaid rear transition metal compound is FeCl
2, CoCl
2Or NiBr
2(DME).
The rear transition metal organic catalyst of the present invention's preparation is used for ethylene polymerization.
Advantage of the present invention is as follows:
1, can change neatly substituted radical and rear transition metal compound.
2, reaction conditions is gentle, and is insensitive to oxygen, water.
3, reaction process is simple, productive rate is higher.
4, set up the synthetic method of Click part, open up the novel method of a kind of synthesizing new bidentate title complex and CGC type catalyzer, the condition of necessity is provided for the polyolefine new variety of exploitation superior performance.
Embodiment
Embodiment 1
At 20mLN, dinethylformamide/water mol ratio is in the mixed solution of 4:1, adds successively benzyl chloride (0.50mL, 4.4mmol), sodiumazide (0.30g, 4.8mmol), 2-ethynyl pyridine (0.40mL, 4.0mmol) obtains the solution of reaction mixture; Solution at reaction mixture can add anhydrous sodium carbonate (0.61g successively, 5.76mmol), xitix (0.84g, 4.8mmol), copper sulfate (0.492g, 2.4mmol), at normal temperatures and pressures behind the stirred reaction mixture 20h, become yellow turbid liquid, use the ethyl acetate extraction organic phase, and use distilled water wash.The organic phase anhydrous sodium sulfate drying removes by filter anhydrous sodium sulphate, is spin-dried for solvent, obtains the ligand compound of 0.726g water white transparency solid, productive rate 77%.
Under the nitrogen protection, in reaction flask, add the 20mL dichloromethane solution; by ligand compound: the FeCl2 mol ratio is 1:1, adds ligand compound (0.36g, 1.54mmol) and FeCl2 (0.19g; 1.54mmol), under nitrogen protection, normal temperature and pressure, react 1.5h.Leave standstill, filter out supernatant liquid, remaining solid is drained under vacuum, with obtaining 1.729g yellow-green colour solid C14H12Cl2FeN4 after the normal hexane washing, productive rate is 94.6% again.
Embodiment 2
At 20mLN, dinethylformamide/water mol ratio is in the mixed solution of 3.6:1, add benzyl chloride (0.52mL, 4.6mmol), sodiumazide (0.30g, 4.8mmol), 2-ethynyl pyridine (0.40mL, 4.0mmol), anhydrous sodium carbonate (0.63g, 5.95mmol), then add xitix (0.84g, 4.8mmol), copper sulfate (0.492g, 2.4mmol), under the room temperature behind the stirred reaction mixture 20h, become yellow turbid liquid, use the ethyl acetate extraction organic phase, and use distilled water wash.The organic phase anhydrous sodium sulfate drying removes by filter anhydrous sodium sulphate, is spin-dried for solvent, obtains 0.715g water white transparency solid, productive rate 75.8%.
Under the nitrogen protection, in reaction flask, add the 20mL dichloromethane solution; by ligand compound: the CoCl2 mol ratio is 1:1.05, adds ligand compound (0.31g, 1.30mmol) and CoCl2 (0.176g; 1.36mmol), under nitrogen protection, normal temperature and pressure, react 2h.Leave standstill, filter out supernatant liquid, remaining solid is drained under vacuum, with obtaining 0.37g blue solid C14H12Cl2CoN4 after the normal hexane washing, productive rate is 80% again.
Embodiment 3
At 20mLN, dinethylformamide/water mol ratio is in the mixed solution of 3.5:1, add benzyl chloride (0.53mL, 4.72mmol), sodiumazide (0.30g, 4.8mmol), 2-ethynyl pyridine (0.40mL, 4.0mmol), anhydrous sodium carbonate (0.636g, 6.0mmol), then add xitix (0.84g, 4.8mmol), copper sulfate (0.492g, 2.4mmol), under the room temperature behind the stirred reaction mixture 20h, become yellow turbid liquid, use the ethyl acetate extraction organic phase, and use distilled water wash.The organic phase anhydrous sodium sulfate drying removes by filter anhydrous sodium sulphate, is spin-dried for solvent, obtains 0.70g water white transparency solid, productive rate 74.2%.
Under the nitrogen protection; in reaction flask; add the 20mL dichloromethane solution; be 1:1.1 by ligand compound: NiBr2 (DME) mol ratio; add ligand compound (0.24g; 0.99mmol) and NiBr2 (DME) (0.336g, 1.09mmol), under nitrogen protection, normal temperature and pressure, react 1.7h.Leave standstill, filter out supernatant liquid, remaining solid is drained under vacuum, with obtaining the light brown solid C14H12Br2NiN4 of 0.35g after the normal hexane washing, productive rate is 65% again.
The relevant characterization of gained late transition metal complex catalyst is as follows:
(1) sign take benzyl chloride, sodiumazide, 2-ethynyl pyridine as raw material gained ligand compound
Fusing point: 95 ℃.
1H?NMR（CDCl
3,298K，300MHz.）：δ(ppm)7.76(1H，=CH-oftriazole)，7.33-7.38(4H，Py)，7.31-7.33(5H，Ph)。
13C?NMR（CDCl
3,298K，75MHz.）：δ(ppm)129.31-134.51(2C，triazole)，137.05(1C，Ph)，137.06-150.38(5C，Py)，120.38-128.98(5C，Ph)，54.52(1C，-CH
2-)。IR(KBr；cm
-1)：3104.9，2948.9，2164.9，2030.1，1978.5，1709.4，1599.1，1571.3，1544.8，1492.9，1455.8，1434.5，1346.9，1210.9，1151.0，1077.2，1041.6，901.9，854.0，780.8，706.6。Ultimate analysis (mass percent %), C
14H
12N
4: theoretical value C 71.17, and H 5.12, and N 23.71; Measured value C 69.77, H 5.10, and N 23.04.
Table 1 is the crystal data of this ligand compound.
(2) take benzyl chloride, sodiumazide, 2-ethynyl pyridine as raw material gained ligand compound and FeCl
2The sign of the title complex that effect obtains
Fusing point: 155 ℃.IR(KBr；cm
-1)：3094.6，3046.1，3017.8，2962.4，2166.3，1978.5，1608.7，1572.5，1474.6，1450.0，1427.4，1365.2，1214.2，1158.8，1040.9，1013.8，907.7，874.8，752.5，733.4，721.2，696.5。Ultimate analysis (mass percent %), C
14H
12Cl
2FeN
4: theoretical value C 46.32, and H 3.33, and N 15.43; Measured value C 47.72, H 3.83, and N 15.48.
(3) take benzyl chloride, sodiumazide, 2-ethynyl pyridine as raw material gained ligand compound and CoCl
2The sign of the title complex that effect obtains
Fusing point: 189-190 ℃.IR(KBr；cm
-1)：3416.6，3180.5，3015.8，2166.8，1980.4，1609.6，1573.3，1477.3，1453.3，1363.4，1338.5，1207.9，1154.7，1112.7，1058.6，1052.4，1023.1，989.0，916.4，877.2，730.0，699.6，653.3。Ultimate analysis (mass percent %), C
14H
12Cl
2CoN
4: theoretical value C 45.93, and H 3.30, and N 15.30; Measured value C 47.31, H 3.79, and N 15.77.
(4) take benzyl chloride, sodiumazide, 2-ethynyl pyridine as raw material gained ligand compound and NiBr
2(DME) sign of the title complex that obtains of effect
Fusing point: greater than 300 ℃.IR(KBr；cm
-1)：3329.6，3081.2，3027.0，2164.4，1978.6，1612.0，1577.9，1478.7，1449.3，1427.5，1364.3，1337.7，1266.8，1214.7，1204.0，1155.4，1113.8，1095.0，1078.8，1057.2，1017.9，992.2，914.5，870.2，731.5，695.2。Ultimate analysis (mass percent %), C
14H
12Br
2NiN
4: theoretical value C 36.97, H2.66, and N 12.32; Measured value C 36.03, H 3.04, and N 11.71.
Claims (3)
1. the synthetic method of a late transition metal complex catalyst is characterized in that comprising the steps:
(1) presses DMF: H
2The mol ratio of O is 3.5～4:1, and DMF is mixed with water, obtain DMF and water mixed solution, by benzyl chloride: sodiumazide: 2-ethynyl pyridine mol ratio is 1.1～1.2:1.1～1.2:1, at DMF and H
2In the mixing solutions of O, add successively benzyl chloride, sodiumazide, 2-ethynyl pyridine, obtain the solution of reaction mixture;
(2) by anhydrous sodium carbonate: xitix: the copper sulfate mol ratio is 2.4～2.5:2:1, adds successively anhydrous sodium carbonate, xitix, copper sulfate in the solution of reaction mixture, reacts at normal temperatures and pressures 20～24h;
(3) after the reaction, in reaction system, add ethyl acetate, extracted organic phase, in organic phase, add again the distilled water wash organic phase, and carry out drying with anhydrous sodium sulphate, after anhydrous sodium sulphate is filtered out, steam ethyl acetate solvent, namely obtain the ligand compound take pyridine as parent;
(4) under the nitrogen protection; in reactor, add dichloromethane solution; by ligand compound: the mol ratio of rear transition metal compound is 1:1～1.1; add ligand compound and rear transition metal compound; under nitrogen protection, normal temperature and pressure, react 1.5～2h, leave standstill, filter out supernatant liquid; remaining solid is drained under vacuum, again with obtaining late transition metal complex catalyst after the normal hexane washing.
2. the synthetic method of unification kind late transition metal complex catalyst as claimed in claim 1 is characterized in that described DMF: H
2The mol ratio of O is 4:1.
3. the synthetic method of unification kind late transition metal complex catalyst as claimed in claim 1 is characterized in that described rear transition metal compound thing is FeCl
2, CoCl
2Or NiBr
2(DME).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6043363A (en) * | 1998-03-09 | 2000-03-28 | Symyx Technologies, Inc. | Substituted aminomethylphosphines, compositions and coordination complexes of same, their synthesis and processes using same |
| WO2002066425A2 (en) * | 2001-02-16 | 2002-08-29 | San Diego State University Foundation | Compositions and methods for hydration of terminal alkynes |
| EP1507783B1 (en) * | 2002-05-27 | 2006-12-27 | Degussa AG | Hydroxy diphosphines and their use in catalysis |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6043363A (en) * | 1998-03-09 | 2000-03-28 | Symyx Technologies, Inc. | Substituted aminomethylphosphines, compositions and coordination complexes of same, their synthesis and processes using same |
| WO2002066425A2 (en) * | 2001-02-16 | 2002-08-29 | San Diego State University Foundation | Compositions and methods for hydration of terminal alkynes |
| EP1507783B1 (en) * | 2002-05-27 | 2006-12-27 | Degussa AG | Hydroxy diphosphines and their use in catalysis |
Non-Patent Citations (1)
| Title |
|---|
| 秦璐等，: "2-（1-苄基-1H-1,2,3-***-4-吡啶及其镍(II)配合物的合成及结构的确定", 《山西大学学报自然科学版》 * |
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Application publication date: 20130130 |