CN101773856A - Oxazoline Schiff base ligand metal complex catalyst and application thereof - Google Patents
Oxazoline Schiff base ligand metal complex catalyst and application thereof Download PDFInfo
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- CN101773856A CN101773856A CN201010034468A CN201010034468A CN101773856A CN 101773856 A CN101773856 A CN 101773856A CN 201010034468 A CN201010034468 A CN 201010034468A CN 201010034468 A CN201010034468 A CN 201010034468A CN 101773856 A CN101773856 A CN 101773856A
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Abstract
The invention relates to an oxazoline Schiff base ligand metal complex catalyst and application thereof, belonging to the technical field of chiral catalysts. The oxazoline Schiff base ligand metal complex catalyst is prepared by mixing and stirring an amido oxazoline derivative and a salicylic aldehyde derivative in an organic solvent, and then adding the same mole of cupric acetate and stirring for 0.5-2 hours; an oxazoline Schiff base ligand can also be substituted for the mixture of the amido oxazoline derivative and the salicylic aldehyde derivative of the same mole; and when the oxazoline Schiff base ligand metal complex catalyst is used for catalyzing asymmetric Henry reaction of aldehyde, a chiral nitroalcohol derivative can be obtained. The oxazoline Schiff base ligand metal complex catalyst of the invention has the advantages of easy preparation, low prices of raw materials, simple preparation method, mild conditions and better catalytic activity.
Description
Technical field
Yi Zhong oxazoline Schiff base ligand metal complex catalyst of the present invention and application thereof belong to technical field of chiral catalysts.
Background technology
Along with pharmaceuticals industry, agricultural chemicals, spices and material industry demand growth, develop new chiral catalyst and asymmetry catalysis method and caused extensive concern with the chiral technology that obtains chipal compounds to chipal compounds.The key technology of asymmetry catalysis synthesizing chiral compound is how to design and synthesize the chiral catalyst with high catalytic activity.From at present domestic and international present Research, the chiral catalyst that can be applicable to all kinds of organic chemical reactionses still is few, and the chiral catalyst of excellent performance is protected by foreign patent mostly.Therefore, develop chiral catalyst efficient high selectivity, that have independent intellectual property right, can promote the scientific research and the industrial development of China's chiral technology.Seek a kind of not only convenient preparation, skeleton structure can regulate, but also the chiral catalyst with good catalytic have crucial value for chirality study on the synthesis and commercial Application.In recent years, the chiral oxazoline metal complex is owing to the good catalytic that they are shown in various asymmetric reactions has obtained extensive use.West Buddhist alkali has also obtained extensive use as the important compound of a class in material, medicine and asymmetric catalysis field.And the research that utilizes chiral oxazoline to combine with corresponding western Buddhist alkali to obtain chiral oxazoline Schiff base ligand and catalyst and use also few, therefore, molecular structure fragment and metal ion that chiral oxazoline and western Buddhist alkali two classes are important organically combine with the chiral catalyst of synthesizing new, and it is crucial expanding their application in chipal compounds is synthetic.
The preparation method of oxazoline Schiff base ligand and ammonia oxazolin derivs is 200910243751.5 referring to patent " the oxazoline Schiff base ligand and preparation method thereof " patent No. among the Ben Faming, and structural formula of oxazoline Schiff base ligand is as the formula (1) in it:
Wherein, R
1Be hydrogen, alkyl or aryl; R
2Be hydrogen, nitro, halogen, alkyl or aryl; Alkyl is methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, the tert-butyl group or benzyl, is preferably methyl, isopropyl, the tert-butyl group and benzyl; Aryl is phenyl, naphthyl or xenyl.
Summary of the invention
The objective of the invention is for Yi Zhong oxazoline Schiff base ligand metal complex catalyst and application thereof are provided.
The objective of the invention is to be achieved through the following technical solutions.
Yi Zhong oxazoline Schiff base ligand metal complex catalyst of the present invention, the method for preparing this catalyst is: in organic solvent, the An oxazolin derivs is mixed with moles such as salicylic aldehyde derivative, under 10～35 ℃ of conditions, stir, 0.5 add equimolar copper acetate after～2 hours, stir 0.5～2 hour De again Dao the oxazoline Schiff base ligand metal complex catalyst; Wherein organic solvent is methyl alcohol, ethanol, isopropyl alcohol, ether, benzene, toluene, oxolane, t-butyl methyl ether or carrene, the preparation feedback equation as the formula (2):
Above-mentioned this Preparation of catalysts method Hai Ke Yi Yong oxazoline Schiff base ligand replaces An oxazolin derivs and the equimolar mixture of salicylic aldehyde derivative; The preparation feedback equation is as the formula (3):
The application of the oxazoline Schiff base ligand metal complex catalyst of Ben Faming:
The oxazoline Schiff base ligand metal complex catalyst is used for the asymmetric Henry reaction of catalysis aldehyde, can obtain chiral nitroalcohol derivative.
Beneficial effect
The oxazoline Schiff base ligand metal complex catalyst of Ben Faming is easy to preparation, raw materials used low price, and the preparation method is simple, mild condition, the oxazoline Schiff base ligand metal complex catalyst has catalytic activity preferably.
The specific embodiment
Further describe the present invention below in conjunction with specific embodiment, but the invention is not restricted to following embodiment.
Embodiment 1
The preparation Ia of 1) oxazoline Schiff base ligand, the preparation of embodiment 1 Zhong oxazoline Schiff base ligand Ia in the same patent of its concrete preparation method " Yi Zhong oxazoline Schiff base ligand and preparation method thereof ";
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst i:
In the 10mL reaction tube, add 19.4mg oxazoline Schiff base ligand Ia, 9.1mg copper acetate and 2mL ethanol, stirring at room 30min, De is Dao oxazoline Schiff base ligand metal complex catalyst i;
The application of oxazoline Schiff base ligand metal complex catalyst i:
0.5mmol paranitrobenzaldehyde and 0.26mL nitromethane are joined among the prepared De oxazoline Schiff base ligand metal complex catalyst i, stirring at room 24 hours, concentrate, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtain 101mg (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol, productive rate 95%, record 56%ee by high performance liquid chromatography, chiral column: Daicel Chiralcel OD-H post, isopropyl alcohol: n-hexane=20: 80,1.0mL/min), retention time: t
Minor=11.1min, t
Major=13.3min.
Embodiment 2
The preparation of 1) oxazoline Schiff base ligand Ib, the preparation of the same patent of its concrete preparation method " Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 2 Zhong oxazoline Schiff base ligand Ib;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst ii:
In the 10mL reaction tube, add 20.1mg oxazoline Schiff base ligand Ib, 9.1mg copper acetate and 2mL ethanol, stirring at room 30min, De is Dao oxazoline Schiff base ligand metal complex catalyst ii;
The application of oxazoline Schiff base ligand metal complex catalyst ii:
0.5mmol paranitrobenzaldehyde and 0.26mL nitromethane are joined among the prepared De oxazoline Schiff base ligand metal complex catalyst ii, stirring at room 24 hours, concentrate, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains 100mg (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol, productive rate 94% records 62%ee by high performance liquid chromatography.
Embodiment 3
The preparation of 1) oxazoline Schiff base ligand Ic, the preparation of the same patent of its concrete preparation method " Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 3 Zhong oxazoline Schiff base ligand Ic;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst iii:
In the 10mL reaction tube, add 17.7mg oxazoline Schiff base ligand Ic, 9.1mg copper acetate and 2mL ethanol, stirring at room 30min, De is Dao oxazoline Schiff base ligand metal complex catalyst iii;
The application of oxazoline Schiff base ligand metal complex catalyst iii:
0.5mmol paranitrobenzaldehyde and 0.26mL nitromethane are joined among the prepared De oxazoline Schiff base ligand metal complex catalyst iii, stirring at room 24 hours, concentrate, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains 99mg (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol, productive rate 93% records 57%ee by high performance liquid chromatography.
Embodiment 4
The preparation of 1) oxazoline Schiff base ligand Id, the preparation of the same patent of its concrete preparation method " Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 3 Zhong oxazoline Schiff base ligand Id;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst iv:
In the 10mL reaction tube, add 18.4mg oxazoline Schiff base ligand Id, 9.1mg copper acetate and 2mL ethanol, stirring at room 30min, De is Dao oxazoline Schiff base ligand metal complex catalyst iv;
The application of oxazoline Schiff base ligand metal complex catalyst iv:
0.5mmol paranitrobenzaldehyde and 0.26mL nitromethane are joined among the prepared De oxazoline Schiff base ligand metal complex catalyst iv, stirring at room 24 hours, concentrate, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains 101mg (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol, productive rate 95% records 70%ee by high performance liquid chromatography.
Embodiment 5
The preparation of 1) An oxazolin derivs 4a, 2-[(4S among the same patent of its concrete preparation method " the Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 1)-and 4-phenyl-2-oxazolinyl] preparation of aniline 4a;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst v:
In the 10mL reaction tube, add 2-[(4S)-4-phenyl-2-oxazolinyl] aniline 4a (11.9mg, 0.05mmo1), 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) and ethanol (2mL), stirring at room 30min, (9.1mg 0.05mmol), stirs 30min again and obtains catalyst v to add copper acetate again.
The application of oxazoline Schiff base ligand metal complex catalyst v:
With paranitrobenzaldehyde (76mg, 0.5mmol) and nitromethane (0.26mL, 5.0mmol) add respectively among the prepared De oxazoline Schiff base ligand metal complex catalyst v, stirring at room 24 hours concentrates, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains (1R)-2-nitro-1-(4-nitrobenzophenone) alcohol 95 mg, productive rate 90% records 42%ee by high performance liquid chromatography.
Embodiment 6
The preparation of 1) An oxazolin derivs 4b, 2-[(4S among the same patent of its concrete preparation method " the Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 2)-and 4-benzyl-2-oxazolinyl] preparation of aniline 4b;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst vi:
In the 10mL reaction tube, add 2-[(4S)-4-benzyl-2-oxazolinyl] aniline 4b (12.6mg, 0.05mmol), 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) and ethanol (2mL), stirring at room 30min, (9.1mg 0.05mmol), stirs 30min again and obtains catalyst vi to add copper acetate again.
The application of oxazoline Schiff base ligand metal complex catalyst vi:
With paranitrobenzaldehyde (76mg, 0.5mmol) and nitromethane (0.26mL, 5.0mmol) add respectively among the prepared De oxazoline Schiff base ligand metal complex catalyst vi, stirring at room 24 hours concentrates, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 96mg, productive rate 90% records 62%ee by high performance liquid chromatography.
Embodiment 7
The preparation of 1) An oxazolin derivs 4c, 2-[(4S among the same patent of its concrete preparation method " the Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 3)-and 4-isopropyl-2-oxazolinyl] preparation of aniline 4c;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst vii:
In the 10mL reaction tube, add 2-[(4S)-4-isopropyl-2-oxazolinyl] aniline 4c (10.2mg, 0.05mmol), 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) and ethanol (2mL), stirring at room 30min, (9.1mg 0.05mmol), stirs 30min again and obtains catalyst vii to add copper acetate again.
The application of oxazoline Schiff base ligand metal complex catalyst vii:
With paranitrobenzaldehyde (76mg, 0.5mmol) and nitromethane (0.26mL, 5.0mmol) add respectively among the prepared De oxazoline Schiff base ligand metal complex catalyst vii, stirring at room 24 hours concentrates, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 96mg, productive rate 90% records 62%ee by high performance liquid chromatography.
Embodiment 8
The preparation of 1) An oxazolin derivs 4d, 2-[(4S among the same patent of its concrete preparation method " the Yi Zhong oxazoline Schiff base ligand and preparation method thereof " embodiment 4)-and the 4-tert-butyl group-2-oxazolinyl] preparation of aniline 4d;
The preparation of 2) oxazoline Schiff base ligand metal complex catalyst viii:
In the 10mL reaction tube, add 2-[(4S)-the 4-tert-butyl group-2-oxazolinyl] aniline 4d (10.9mg, 0.05mmol), 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) and ethanol (2mL), stirring at room 30min, (9.1mg 0.05mmol), stirs 30min again and obtains catalyst viii to add copper acetate again.
The application of oxazoline Schiff base ligand metal complex catalyst viii:
With paranitrobenzaldehyde (76mg, 0.5mmol) and nitromethane (0.26mL, 5.0mmol) add respectively among the prepared De oxazoline Schiff base ligand metal complex catalyst viii, stirring at room 24 hours concentrates, silica gel column chromatography separates, solvent is the mixture of benzinum and ethyl acetate, benzinum: the ratio of ethyl acetate is 5: 1, obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 96mg, productive rate 90% records 69%ee by high performance liquid chromatography.
Embodiment 9
1) with among the embodiment 8 the 1st) step;
2) with among the embodiment 8 the 2nd) step; The difference is that and change etoh solvent into ether De Dao oxazoline Schiff base ligand metal complex catalyst viii, the same reaction of catalysis obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 97mg, and productive rate 92% records 82%ee by high performance liquid chromatography.
Embodiment 10
1) with among the embodiment 8 the 1st) step;
2) with among the embodiment 8 the 2nd) step; The difference is that 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) change salicylide (6.1mg into, 0.05mmol) Zhi Bei oxazoline Schiff base ligand metal complex catalyst ix, the same reaction of catalysis obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 98mg, productive rate 93% records 49%ee by high performance liquid chromatography.
Embodiment 11
1) with among the embodiment 8 the 1st) step;
2) with among the embodiment 8 the 2nd) step; The difference is that 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) change 3-methoxysalicyl aldehyde (7.0mg into, 0.05mmol) Zhi Bei oxazoline Schiff base ligand metal complex catalyst x, the same reaction of catalysis obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 103mg, productive rate 98% records 27%ee by high performance liquid chromatography.
Embodiment 12
1) with among the embodiment 8 the 1st) step;
2) with among the embodiment 8 the 2nd) step; The difference is that 5-nitrosalicylaldehyde (8.4mg, 0.05mmol) change 3 into, 5-tert-butyl group salicylide (11.7mg, 0.05mmol) Zhi Bei oxazoline Schiff base ligand metal complex catalyst xi, the same reaction of catalysis obtains (1R)-2-nitro-1-(4-nitrobenzophenone) ethanol 97mg, productive rate 92% records 64%ee by high performance liquid chromatography.
Embodiment 13
1) with among the embodiment 8 the 1st) step;
2) with among the embodiment 8 the 2nd) step; The difference is that and change etoh solvent into ether Zhi Bei oxazoline Schiff base ligand metal complex catalyst viii, with paranitrobenzaldehyde (76mg, 0.5mmol) change special valeral (43mg into, 0.5mmol) carry out catalytic reaction, obtain (S)-3,3-dimethyl-1-nitro-2-butanols 60mg, productive rate 81%, record 92%ee by high performance liquid chromatography, chiral column: Daicel Chiralcel OD-H post, isopropyl alcohol: n-hexane=5: 95,0.8mL/min), retention time: tminor=10.6min, tmajor=12.0min.
Claims (4)
1. Yi Zhong oxazoline Schiff base ligand metal complex catalyst, it is characterized in that the method for preparing this catalyst is: in organic solvent, the An oxazolin derivs is mixed with moles such as salicylic aldehyde derivative, under 10～35 ℃ of conditions, stir, 0.5 add equimolar copper acetate after～2 hours, stir 0.5～2 hour De again Dao the oxazoline Schiff base ligand metal complex catalyst; The preparation feedback equation is as the formula (2):
2. Yi Zhong oxazoline Schiff base ligand metal complex catalyst according to claim 1 is characterized in that: Ke Yi Yong oxazoline Schiff base ligand replaces An oxazolin derivs and the equimolar mixture of salicylic aldehyde derivative; The preparation feedback equation is as the formula (3):
3. Yi Zhong oxazoline Schiff base ligand metal complex catalyst according to claim 1, it is characterized in that: organic solvent is methyl alcohol, ethanol, isopropyl alcohol, ether, benzene, toluene, oxolane, t-butyl methyl ether or carrene.
4. the application of an oxazoline Schiff base ligand metal complex catalyst of stating as claim 1, it is characterized in that: oxazoline Schiff base ligand metal complex catalyst is used for the asymmetric Henry reaction of catalysis aldehyde, can obtain chiral nitroalcohol derivative.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014118799A1 (en) | 2013-02-01 | 2014-08-07 | Council Of Scientific & Industrial Research | Recyclable chiral catalyst for asymmetric nitroaldol reaction and process for the preparation thereof |
| CN106496155A (en) * | 2016-10-31 | 2017-03-15 | 中国农业大学 | A kind of aminothiazole quinoline chiral ligand and its preparation method and application |
| CN107955030A (en) * | 2017-12-12 | 2018-04-24 | 新泰中学 | Chiral aluminum complex containing acetylacetone,2,4-pentanedione derivative and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2308415A1 (en) * | 1997-11-12 | 1999-05-20 | The Penn State Research Foundation | Transition metal-catalyzed reactions based on chiral amine oxazolinyl ligands |
| CN100389117C (en) * | 2004-08-20 | 2008-05-21 | 中国科学院上海有机化学研究所 | Oxazolinyl ring metal catalyst with chiral center, synthesis and use thereof |
| CN101519384A (en) * | 2008-03-28 | 2009-09-02 | 合肥工业大学 | Chiral oxazoline and synthesis method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014118799A1 (en) | 2013-02-01 | 2014-08-07 | Council Of Scientific & Industrial Research | Recyclable chiral catalyst for asymmetric nitroaldol reaction and process for the preparation thereof |
| CN106496155A (en) * | 2016-10-31 | 2017-03-15 | 中国农业大学 | A kind of aminothiazole quinoline chiral ligand and its preparation method and application |
| CN107955030A (en) * | 2017-12-12 | 2018-04-24 | 新泰中学 | Chiral aluminum complex containing acetylacetone,2,4-pentanedione derivative and its preparation method and application |
| CN107955030B (en) * | 2017-12-12 | 2020-09-08 | 新泰中学 | Chiral aluminum complex containing acetylacetone derivative, and preparation method and application thereof |
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