CN102206212B - Preparation and synthesis method for chiral oxazoline - Google Patents
Preparation and synthesis method for chiral oxazoline Download PDFInfo
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- CN102206212B CN102206212B CN 201110085506 CN201110085506A CN102206212B CN 102206212 B CN102206212 B CN 102206212B CN 201110085506 CN201110085506 CN 201110085506 CN 201110085506 A CN201110085506 A CN 201110085506A CN 102206212 B CN102206212 B CN 102206212B
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Abstract
The invention relates to a preparation and synthesis method for chiral oxazoline, which is 1-[2-(4-phenyl-4,5-dihydro-2-oxazolinyl)]-ethyl-2-pyrrolidone with a chemical structural formula as shown in the specification. The synthesis method of the chiral oxazoline comprises the steps of reaction, separation and purification, and is characterized by: carrying out reflux reaction in chlorobenzene used as a solvent on 3-[1-(2-carbonyl) pyrrolidyl]-propionitrile and D-phenylglycinol under a water-free oxygen-free condition in the presence of anhydrous ZnCl2 used as a catalyst for 24 hours, separating and purifying, namely removing chlorobenzene after reaction, adding water for dissolving, extracting with chloroform, removing the solvent from an extraction phase and purifying through column chromatography. The chiral oxazoline presents good catalysis effect in the nitrile silicification reaction of 2-methyl benzaldehyde.
Description
One, technical field
The present invention relates to a kind of chipal compounds and purposes, specifically a kind of preparation of chiral oxazoline and synthetic method.
Two, background technology
The title complex of chiral oxazoline and metal (shows the active and high enantioselectivity of good asymmetry catalysis, thereby is paid close attention to widely at Didls-Alder in the many reactions such as diene cycloaddition reaction, Michael (Mi Xieer) condensation reaction, Friedel-Crafts (Fu Ruide-carat Buddhist now) condensation reaction, Aldol (alcohol aldehyde) condensation reaction of Di Lesi-Ai Erte).
Three, summary of the invention
The present invention is intended to provide a kind of efficient chiral catalyst for the asymmetric synthesis field particularly prepares the chiral drug compound, technical problem to be solved be select and the synthesis of chiral part with the preparation composition catalyst.
The alleged chiral oxazoline of the present invention be chemical name be 1-[2-(4-phenyl-4,5-dihydro-2-oxazolinyl]-ethyl-2-tetramethyleneimine copper, be the compound shown in the following chemical formula (I):
This chiral oxazoline compound (I) has shown catalytic effect preferably at the nitrile silicification reaction of 2-tolyl aldehyde.
The synthetic method of this chipal compounds is with 3-[1-(2-carbonyl) pyrrolidyl]-propionitrile be feedstock production 1-[2-(4-phenyl-4,5-dihydro-2-oxazolinyl]-ethyl-2-tetramethyleneimine copper, flow process schematically as follows:
The synthetic method of this chiral oxazoline comprises reaction, separation and purifying, it is characterized in that the pyrrolidyl by 3-[1-(2-carbonyl)]-propionitrile and D-benzene glycinol be under the anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2When existing in chlorobenzene solvent back flow reaction 24 hours, separate then, purifying, i.e. reaction is sloughed chlorobenzene after finishing, chloroform extraction is used in the back that is dissolved in water, and uses column chromatography purification behind the extraction phase precipitation.
Four, description of drawings
Fig. 1, Fig. 2 are respectively the chiral oxazoline compound I
1HNMR figure and
13CNMR figure.
Five, embodiment
(the preparation of a) chiral oxazoline compound I
In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl
22g (14.7mmol), 40mL chlorobenzene, 3-[1-(2-carbonyl) pyrrolidyl]-propionitrile 6.3g, D-benzene glycinol 10g, with the mixture 24h that at high temperature refluxes, stopped reaction, decompression is with desolventizing,, with the residuum water dissolution, and use CHCl
3(20mLx2) extraction, the organic phase anhydrous sodium sulfate drying, the rotation desolventizing with sherwood oil/methylene dichloride (4: 1) column chromatography, gets colourless oil liquid productive rate 60% with thick product; [a]
5 D=+40.2 ° of (c=0.298, CH
2Cl
2):
1HNMR (300MHz, CDCl
3, 27 ℃), δ (ppm)=7.24～7.37 (m, 5H), 5.17 (t, J=0.3Hz, 1H), 4.59～4.66 (m, 1H), 4.11 (t, 1H), 3.46 (t, J=0.9Hz, 2H), 2.65 (t, 3H), 2.38 (t, 3H), 1.99～2.04 (m, 6H);
13CNMR, 17.72,26.20,30,65,39.21,47.05,69.38,74.37,126.33,127.31,128.43,141.87,166.07,174.84.IR (KBr compressing tablet): 3436,3029,2932,1733,1682,1494,1454,1385,1425,1378,1288,1226,1172,986,924,849,762,702,655,563,532,494.HRMS(EI)：m/z(％)：calcd?for?C
15H
18N
2O
2：258.1368；found：258.1373。
(2) 2-o-tolyl-2-(three silyloxies) acetonitrile
0.2mmol chiral oxazoline compound I (1mmol), 2-tolyl aldehyde 0.1mmol, TMSCN0.3ml (3.3mmol) add down at 20～30 ℃ in succession, after 5 days, add water cancellation (sherwood oil/methylene dichloride: 5/1), get colourless oil liquid behind the post layer.Transformation efficiency:＞99%.
Claims (2)
1. chiral oxazoline is characterized in that: by following chemical formulation:
2. the synthetic method by the described chiral oxazoline of claim 1 comprises reaction, separation and purifying, it is characterized in that 3-[1-(2-carbonyl) pyrrolidyl]-propionitrile and D-benzene glycinol be under the anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2When existing in chlorobenzene solvent back flow reaction 24 hours, separate then, purifying, i.e. reaction is sloughed chlorobenzene after finishing, chloroform extraction is used in the back that is dissolved in water, and uses column chromatography purification behind the extraction phase precipitation, catalyst levels is 1～3wt% of material quantity.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110085506 CN102206212B (en) | 2011-04-06 | 2011-04-06 | Preparation and synthesis method for chiral oxazoline |
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| CN 201110085506 CN102206212B (en) | 2011-04-06 | 2011-04-06 | Preparation and synthesis method for chiral oxazoline |
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| CN102206212B true CN102206212B (en) | 2013-07-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255493B1 (en) * | 1997-11-12 | 2001-07-03 | The Penn State Research Foundation | Transition metal-catalyzed reactions based on chiral amine oxazolinyl ligands |
| CN101824031A (en) * | 2010-05-17 | 2010-09-08 | 合肥工业大学 | Chiral oxazoline and use thereof |
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2011
- 2011-04-06 CN CN 201110085506 patent/CN102206212B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255493B1 (en) * | 1997-11-12 | 2001-07-03 | The Penn State Research Foundation | Transition metal-catalyzed reactions based on chiral amine oxazolinyl ligands |
| CN101824031A (en) * | 2010-05-17 | 2010-09-08 | 合肥工业大学 | Chiral oxazoline and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| Luo Mei等.Synthesis of Novel Oxazolines and Application in Cyanosilylation of Prochiral Ketones.《Heteroatom Chemistry》.2007,第18卷(第6期),第679-683页. |
| Synthesis of Novel Oxazolines and Application in Cyanosilylation of Prochiral Ketones;Luo Mei等;《Heteroatom Chemistry》;20070914;第18卷(第6期);第679-683页 * |
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