CN102199149A - Preparation and synthesis method for chiral oxazoline - Google Patents
Preparation and synthesis method for chiral oxazoline Download PDFInfo
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- CN102199149A CN102199149A CN2011100696438A CN201110069643A CN102199149A CN 102199149 A CN102199149 A CN 102199149A CN 2011100696438 A CN2011100696438 A CN 2011100696438A CN 201110069643 A CN201110069643 A CN 201110069643A CN 102199149 A CN102199149 A CN 102199149A
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- chiral oxazoline
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Abstract
A chiral oxazoline is a 1-[2-(4-isopropyl-4,5-dihydro-2-oxazolinyl)]-ethyl-2-pyrrolidone of which the chemical structural formula is shown in the specification. The synthesis method of the chiral oxazoline comprises the steps of reaction, separation and purification. The synthesis method is characterized by carrying out reaction under reflux in a chlorobenzene solvent, for 24 hours, on 3-[1-(2-carbonyl)pyrrolidyl]-propionitrile and D-valinol in the presence of an anhydrous ZnCl2 catalyst in the absence of water and oxygen; and separating and purifying: removing chlorobenzene after reaction, adding water for dissolving, extracting with chloroform, removing the solvent from the extraction phase and purifying through column chromatography. The chiral oxazoline presents a 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 subjected to paying 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-sec.-propyl-4,5-dihydro-2-oxazolinyl]-ethyl-2-tetramethyleneimine copper, be the compound (I) 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-sec.-propyl-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-valerian ammonia alcohol 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), the 40mL chlorobenzene, 3-(1-hexahydropyridine base)-propionitrile 6.5, D-valerian ammonia alcohol 10g, with the mixture 24h that at high temperature refluxes, stopped reaction, decompression is desolvated to remove,,, and use CHCl with the residuum water dissolution
3(20mLx2) extraction, the organic phase anhydrous sodium sulfate drying, rotation removes and desolvates, and thick product with sherwood oil/methylene dichloride (4: 1) column chromatography, is got colourless oil liquid productive rate 60%; [a]
5 D=+7.67 ° of (c=0.52, CHCl
3):
1HNMR (500MHz, CDCl
3, 27 ℃), and δ (ppm)=4.21～4.26 (m, 1H), 3.84～3.96 (m, 2H), 3.59～3.63 (m, 2H), 3.42～3.56 (m, 2H), 2.52 (t, 2H), 2.36 (t, 2H), 2.02～2.07 (m, 2H), 1.68～1.73 (m, 1H), 0.86～0.97 (dd, J=6.6Hz, 6.6Hz, 2H)
13CNMR, 17.99,18.16,18.81,26.54,30.89,32.54,39.47,47.29,70.17,72.19,165.0l, (174.94.IR KBr compressing tablet): 3304,2957,2871,2234,167l, 1596,1496,1467,1387,1368,1289,1225,1172,1072,986,948,921,850,732,645, HRMS (EI): m/z (%): calcd for C
12H
20N
2O
2: 225.1603; Found:225.1583.HRMS(EI)：m/z(％)：calcd?for?C
14H
26N
2O：238.2045；found：238.2038.
(2) 2-o-tolyl-2-(three silyloxies) acetonitrile
0.2mmol chiral oxazoline Compound I (1mmol), 2-tolyl aldehyde 0.1mmol, TMSCN 0.3ml (3.3mmol) add down at 20～30 ℃ in succession, after 5 days, add shrend go out behind the post layer (sherwood oil/methylene dichloride: 5/1), colourless oil liquid.Transformation efficiency: 99%; Ee%:88%,
1H NMR (300MHz, CDCl3) 7.56-7.59 (m, 0.9Hz, 2H), 7.31-7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H).
13C NMR (75MHz, CDCl3) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).
Claims (2)
1. chiral oxazoline is characterized in that: by following chemical formulation, its chemical name be 1-[2-(4-sec.-propyl-4,5-dihydro-2-oxazolinyl]-ethyl-2-tetramethyleneimine copper, following chemical structural formula is arranged:
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-valerian ammonia alcohol 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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| CN2011100696438A CN102199149A (en) | 2011-03-22 | 2011-03-22 | Preparation and synthesis method for chiral oxazoline |
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| CN2011100696438A CN102199149A (en) | 2011-03-22 | 2011-03-22 | Preparation and synthesis method for chiral oxazoline |
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| CN2011100696438A Pending CN102199149A (en) | 2011-03-22 | 2011-03-22 | Preparation and synthesis method for chiral oxazoline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924440A (en) * | 2012-11-28 | 2013-02-13 | 罗梅 | Preparation and synthesis method of chiral oxazoline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933463A (en) * | 1989-05-08 | 1990-06-12 | Gaf Chemicals Corporation | Polymerizable pyrrolidonyl oxazoline monomers, homopolymers and copolymers |
| CN101279954A (en) * | 2008-05-14 | 2008-10-08 | 合肥工业大学 | Chiral oxazoline and synthetic method thereof |
| CN101824031A (en) * | 2010-05-17 | 2010-09-08 | 合肥工业大学 | Chiral oxazoline and use thereof |
-
2011
- 2011-03-22 CN CN2011100696438A patent/CN102199149A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933463A (en) * | 1989-05-08 | 1990-06-12 | Gaf Chemicals Corporation | Polymerizable pyrrolidonyl oxazoline monomers, homopolymers and copolymers |
| CN101279954A (en) * | 2008-05-14 | 2008-10-08 | 合肥工业大学 | Chiral oxazoline and synthetic method thereof |
| CN101824031A (en) * | 2010-05-17 | 2010-09-08 | 合肥工业大学 | Chiral oxazoline and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Tetrahedron》 20040405 Helen A. McManus 等 Preparation of pyrrolidine-oxazoline containing ligands and their application in asymmetric transfer hydrogenation 全文 1-2 第60卷, 第15期 * |
| HELEN A. MCMANUS 等: "Preparation of pyrrolidine–oxazoline containing ligands and their application in asymmetric transfer hydrogenation", 《TETRAHEDRON》, vol. 60, no. 15, 5 April 2004 (2004-04-05), XP004498830, DOI: doi:10.1016/j.tet.2004.02.038 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924440A (en) * | 2012-11-28 | 2013-02-13 | 罗梅 | Preparation and synthesis method of chiral oxazoline |
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Application publication date: 20110928 |