CN103288662A - Method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity - Google Patents
Method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity Download PDFInfo
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- CN103288662A CN103288662A CN201210499533XA CN201210499533A CN103288662A CN 103288662 A CN103288662 A CN 103288662A CN 201210499533X A CN201210499533X A CN 201210499533XA CN 201210499533 A CN201210499533 A CN 201210499533A CN 103288662 A CN103288662 A CN 103288662A
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- ammonia ester
- enaminone
- alkene ammonia
- alkene
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Abstract
The invention relates to a method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity. Beta-ketone ester (or 1,3-diketone) and amine are adopted as raw materials, 0.25 mol equivalent weight of trimethylchlorosilane is taken as a catalyst, a reaction is carried out for 6 hours at the temperature of 50 DEG C in an ethyl alcohol solvent to obtain corresponding beta-alkene ammonia ester or enaminone, various different ketone esters and similar 1,3-diketone can react with amine to obtain corresponding products, and finally recrystallization or column chromatography is carried out to obtain a pure beta-alkene ammonia ester (aenaminone) product. The method for synthesizing the beta-alkene ammonia ester and enaminone with efficient selectivity has the advantages that firstly raw materials are simple and easy to get, and synthesis conditions are mild; secondly chemical selectivity is highly controllable; and thirdly a catalytic system is wide in applicability, the obtain product is widely applied in the organic synthetic chemistry field, and the method for synthesizing the beta-alkene ammonia ester and enaminone with efficient selectivity is applicable to mass production.
Description
Technical field
The present invention relates to the method for a kind of synthetic β-alkene ammonia ester, relate in particular to the method for the synthetic β of a kind of efficient selective-alkene ammonia ester and enamine ketone.
Background technology
β-alkene ammonia ester comprises that analogue β-alkene ammonia ketone all is important organic compound, has important use in organic chemistry filed.The two is at the small molecules heterogeneous ring compound, is widely used in natural product synthetic, and itself also is structural unit in the organic compound of a lot of biologically actives.β-known synthetic method of alkene ammonia ketone is mainly by Lewis acid such as InCl
3, CeCl
3, oxide compound such as P
2O
5, catalysis 'beta '-ketoester such as nano-ZnO and amine condensation obtain, and be less by the report of cheap catalyst synthetic this compounds under mild conditions.This synthetic method realizes the efficient synthetic of β-alkene ammonia ester and enamine ketone by adopting cheap trimethylchlorosilane as catalyzer, and the scope of application is extensive, and productive rate is good, learns industrial circle at relating to organic and has important application prospects.
Summary of the invention
The method that the object of the present invention is to provide a kind of efficient selective to synthesize β-alkene ammonia ester and enamine ketone, this method cost of material is cheap, and the reaction efficiency height is handled simple; Products therefrom is in synthetic chemistry, and particularly synthesizing of function small molecules heterogeneous ring compound has vital role, has good industrialized application prospect.
The present invention is achieved like this, and method is for adopting 'beta '-ketoester or 1, and 3-diketone and amine are raw material, and 'beta '-ketoester, 1,3-diketone and amine all are 1mmol, and the trimethylchlorosilane of 0.25 molar equivalent is catalyzer, in alcohol solvent 50
oReaction is 6 hours under the C condition, obtains corresponding β-alkene ammonia ester or enamine ketone, obtains pure β-alkene ammonia ester or enamine ketone product by crystallization or column chromatography at last.
Technique effect of the present invention is: 1, raw material is easy is easy to get, the synthesis condition gentleness; 2, the chemo-selective height is controlled; 3, the catalyst system suitability is wide, and products therefrom is widely used in the Synthetic Organic Chemistry field, is applicable to scale operation.
Description of drawings
Fig. 1 is product among the present invention
3aProton nmr spectra.
Fig. 2 is product among the present invention
3bProton nmr spectra.
Fig. 3 is product among the present invention
3cProton nmr spectra.
Fig. 4 is product among the present invention
3dProton nmr spectra.
Fig. 5 is product among the present invention
3eProton nmr spectra.
Fig. 6 is product among the present invention
3fProton nmr spectra.
Embodiment
As Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, shown in Figure 6, the present invention realizes like this, in the round-bottomed flask of 50 mL, add 3 mmol 1 respectively, the primary amine (as aniline) of 3-dicarbonyl compound (as methyl aceto acetate) and 3 mmol, add 5 mL ethanol and 0.75 mmol trimethylchlorosilane (TMSCl) then successively, be reflected at 50
oC stirred 6 hours.The cooling back adds 10 mL water to system, and solid product is directly separated out, and filtration drying gets pure product; For product liquid, with 3 * 10 mL ethyl acetate extractions, steaming desolventizes the pure product of silica gel column chromatography, productive rate 80 ~ 92 % behind the anhydrous sodium sulfate drying.Reaction formula and data are as follows, and all product structures and purity contrast through nucleus magnetic resonance and with the bibliographical information result to be determined.
Claims (1)
1. the method for the synthetic β of an efficient selective-alkene ammonia ester and enamine ketone is characterized in that method is that to adopt 'beta '-ketoester or 1,3-diketone and amine be raw material, 'beta '-ketoester, 1,3-diketone and amine all are 1mmol, and the trimethylchlorosilane of 0.25 molar equivalent is catalyzer, in alcohol solvent 50
oReaction is 6 hours under the C condition, obtains corresponding β-alkene ammonia ester or enamine ketone, obtains pure β-alkene ammonia ester or enamine ketone product by crystallization or column chromatography at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499533.XA CN103288662B (en) | 2012-11-30 | 2012-11-30 | Method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499533.XA CN103288662B (en) | 2012-11-30 | 2012-11-30 | Method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103288662A true CN103288662A (en) | 2013-09-11 |
| CN103288662B CN103288662B (en) | 2015-07-15 |
Family
ID=49090264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210499533.XA Expired - Fee Related CN103288662B (en) | 2012-11-30 | 2012-11-30 | Method for synthesizing beta-alkene ammonia ester and enaminone with efficient selectivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103288662B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252945A (en) * | 1979-07-11 | 1981-02-24 | E. R. Squibb & Sons, Inc. | Process for preparing pyrazolo[1,5-c]-quinazoline derivatives and novel intermediates |
-
2012
- 2012-11-30 CN CN201210499533.XA patent/CN103288662B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252945A (en) * | 1979-07-11 | 1981-02-24 | E. R. Squibb & Sons, Inc. | Process for preparing pyrazolo[1,5-c]-quinazoline derivatives and novel intermediates |
Non-Patent Citations (1)
| Title |
|---|
| CLAUDIA P. CARTAYA-MARIN ET AL: "SYNTHESIS OF ENAMINONES USING TRIMETHYLSILYL TRIFLUOROMETHANESULFONATE AS AN ACTIVATOR", 《SYNTHETIC COMMUNICATIONS》 * |
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| Publication number | Publication date |
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| CN103288662B (en) | 2015-07-15 |
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