CN103570751A - Chiral leucinol copper complex - Google Patents
Chiral leucinol copper complex Download PDFInfo
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- CN103570751A CN103570751A CN201310528507.XA CN201310528507A CN103570751A CN 103570751 A CN103570751 A CN 103570751A CN 201310528507 A CN201310528507 A CN 201310528507A CN 103570751 A CN103570751 A CN 103570751A
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- leucinol
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Abstract
The invention provides a chiral leucinol copper complex (I), having a chemical formula as shown in specification, wherein a synthetic method of the complex (I) comprises the following steps of: reacting (L)-leucinol with copper chloride dihydrate in the mol ratio of 3: 1, weighing 3.8337ml of (0.03mol) of L-leucinol and 2.4908g (0.01mol) of cobaltous acetate hexahydrate by using an electronic scale, putting the weighed L-leucinol and cobaltous acetate hexahydrate in a 100ml round-bottom flask, adding 30ml of methanol as a reaction solvent, heating for reflux and stirring for 48 h; immediately thermally filtering by using a conical flask after the reaction is terminated, sealing by using a preservative film, and standing at the normal temperature until red brown crystals appear in two days. The complex shows good catalytic performance in the Henry reaction of benzaldehyde; and the percent conversion of the complex is 75%.
Description
One, technical field
The present invention relates to a kind of new compound and preparation method thereof, particularly a kind of cobalt compound and preparation method thereof, is exactly a kind of preparation and synthetic method of chirality L-leucinol cupric chloride title complex.
Two, background technology
Chiral amino alcohol copper complex is important catalyzer and medication chemistry product, it is important catalyzer and medication chemistry product as catalyzer chiral amino alcohol copper complex, and it has good catalytic effect as catalyzer in zinc ethyl reacts with phenyl aldehyde enantioselective addition etc.【1-3】
Reference:
1.Hydrophobic-exterior?layer?structures?and?magnetic?properties?of?trinuclear?copper?complexes?with?chiral?amino?alcoholate?ligands，cLaren，Jana?K.；Sanchiz，Joaquin；Gili，Pedro；Janiak，Christoph，New?Journal?of?Chemistry(2012)，36(8)，1596-1609.
2.Highly?enantioselective?Henry?reactions?of?aromatic?aldehydes?catalyzed?by?an?amino?alcohol-copper(II)complex，Qin，Dan-Dan；Lai，Wen-Han；Hu，Di；Chen，Zheng；Wu，An-An；Ruan，Yuan-Ping；Zhou，Zhao-Hui；Chen，Hong-Bin，Chemistry-A?European?Journal(2012)，18(34)，10515-10518
3.Heterogeneous?Chiral?Copper?Complexes?of?Amino?Alcohol?for?Asymmetric?Nitroaldol?Reaction，Mayani，Vishal?J.；Abdi，Sayed?H.R.；Kureshy，Rukhsana?I.；Khan，Noor-ul?H.；Das，Anjan；Bajaj，Hari?C.Journal?of?Organic?Chemistry(2010)，75(18)，6191-6195.
Three, summary of the invention
The present invention aims to provide chirality four [(S)-leucinol] CuCl-compound.Technical problem to be solved is that one-step synthesis obtains target product.
The alleged chirality copper complex of the present invention be by with L-leucinol prepare by the compound shown in following chemical formula:
Chemical name: four [(S)-leucinol] CuCl-compound, is called for short title complex (I).This title complex has shown good catalytic performance in the Henle reaction of phenyl aldehyde, and its transformation efficiency reaches 75%.
This synthetic method comprises synthetic with separated, described synthetic (L)-leucinol reacts with mol ratio 3:1 with Copper dichloride dihydrate, with electronic balance, take 3.8337ml (0.03mol) L-leucinol and 2.4908g (0.01mol) six hydration cobaltous acetates are put into 100ml round-bottomed flask, add 30ml methyl alcohol to do reaction solvent, reflux stirs 48h.After finishing, reaction uses immediately Erlenmeyer flask heat filtering, and with preservative film sealing, standing under normal temperature, there is two days later crystal russet.
With sherwood oil, fully rinse 3-4 time, vacuum-drying 30min, obtains purer target product.
Building-up reactions is as follows:
This synthetic method one step obtains target product, and technique is simple, easy to operate.
Four, accompanying drawing explanation
Fig. 1 is the single X-ray diffractometer figure of chirality four [(S)-leucinol] CuCl-compound.
Five, embodiment
The preparation of chirality four [(S)-leucinol] CuCl-compound:
Take 3.8337ml (0.03mol) L-leucinol and 1.7048g (0.01mol) Copper dichloride dihydrate is put into 100ml round-bottomed flask, adding 30ml methyl alcohol to do reaction solvent, reflux stirs 48h.After reaction finishes, use immediately Erlenmeyer flask heat filtering, be spin-dried for partially liq, standing under normal temperature, there is two days later blue crystal.Product is rinsed 3 times with sherwood oil and normal hexane, the target product after vacuum-drying 30min, productive rate is 43%.Fusing point is 153-155 ℃; [a]
5 d=-262.3 ° of (c=0.064, CH
3oH), ultimate analysis (C
24h
55cu
2n
4o
4), theoretical value is C:45.95%; H:9.00%; N:8.93%.Measured value C:45.85%; H:8.61%; N:8.74%.3397,2958,1613,1509,1470,1389,1369,1172, the crystal data of 1131,1053,991,557 compounds:
The typical bond distance's data of crystal:
The typical bond angle data of crystal
(3), Henle reaction application
(E) preparation of-beta-nitrostyrene
Composition catalyst (I) catalytic amount of getting 0.15mmol is 20% in the little flask of 25mL, add 2 milliliters of absolute methanol solutions, then, in above-mentioned solution, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature, react 6 hours, carry out nmr analysis, transformation efficiency: 75.2%.
1HNMR(300MHz，CDCl
3)，8.00(d，J＝23Hz，1H)，7.47～7.63(m，6H)。
Claims (3)
1. a chirality leucinol cupric chloride title complex (I), its chemical formula is as follows:
2. title complex claimed in claim 1 (I), at 140 (2) k temperature, on Oxford X-ray single crystal diffractometer, with the MoKa ray (λ=0.71073A) through graphite monochromator monochromatization, with w-Theta scan mode, collect diffraction data, it is characterized in that crystal belongs to rhombic system, spacer P2 (1) 2 (1) 2 (1), a=6.1861 (13) A, alpha=90deg; B=20.838 (4) A, beta=90deg; C=28.274 (15) A.gamma=90deg.
3. the synthetic method of title complex claimed in claim 1 (I), comprise synthetic with separated, it is characterized in that described synthetic (L)-leucinol reacts with mol ratio 3:1 with Copper dichloride dihydrate, with electronic balance, take 3.8337ml (0.03mol) L-leucinol and 2.4908g (0.01mol) six hydration cobaltous acetates are put into 100ml round-bottomed flask, add 30ml methyl alcohol to do reaction solvent, reflux stirs 48h.After finishing, reaction uses immediately Erlenmeyer flask heat filtering, and with preservative film sealing, standing under normal temperature, there is two days later crystal russet.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310528507.XA CN103570751A (en) | 2013-10-26 | 2013-10-26 | Chiral leucinol copper complex |
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| CN201310528507.XA CN103570751A (en) | 2013-10-26 | 2013-10-26 | Chiral leucinol copper complex |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819493A (en) * | 2014-03-01 | 2014-05-28 | 合肥工业大学 | A copper nitrogen complex |
| CN104592257A (en) * | 2015-03-10 | 2015-05-06 | 合肥工业大学 | Copper-nitrogen complex |
| CN105566357A (en) * | 2016-03-15 | 2016-05-11 | 合肥祥晨化工有限公司 | Preparation and synthesis method of chiral L-valine copper complex |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718783A (en) * | 2012-07-12 | 2012-10-10 | 罗梅 | Chiral compound |
| CN103285924A (en) * | 2013-07-03 | 2013-09-11 | 罗梅 | Application of chiral copper complex |
-
2013
- 2013-10-26 CN CN201310528507.XA patent/CN103570751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718783A (en) * | 2012-07-12 | 2012-10-10 | 罗梅 | Chiral compound |
| CN103285924A (en) * | 2013-07-03 | 2013-09-11 | 罗梅 | Application of chiral copper complex |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819493A (en) * | 2014-03-01 | 2014-05-28 | 合肥工业大学 | A copper nitrogen complex |
| CN103819493B (en) * | 2014-03-01 | 2015-12-09 | 合肥工业大学 | A kind of copper-nitrogen compound |
| CN104592257A (en) * | 2015-03-10 | 2015-05-06 | 合肥工业大学 | Copper-nitrogen complex |
| CN104592257B (en) * | 2015-03-10 | 2017-06-27 | 合肥工业大学 | A kind of copper-nitrogen compound |
| CN105566357A (en) * | 2016-03-15 | 2016-05-11 | 合肥祥晨化工有限公司 | Preparation and synthesis method of chiral L-valine copper complex |
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Application publication date: 20140212 |