Unlock instant, AI-driven research and patent intelligence for your innovation.
Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system
What is Al technical title?
Al technical title is built by PatSnap Al team. It summarizes the technical point description of the patent document.
A technology for dicarbonyl compounds and palladium compounds, which is applied in the field of preparing 1,3-dicarbonyl compounds based on metal hydride/palladium compound systems, can solve the problems of high atomic economy, explosive hydrogen gas, lack of reaction and the like, and achieves reaction yield. The effect of high rate, low price and low usage
Active Publication Date: 2018-12-11
NANTONG TEXTILE & SILK IND TECH RES INST +1
View PDF4 Cites 3 Cited by
Summary
Abstract
Description
Claims
Application Information
AI Technical Summary
This helps you quickly interpret patents by identifying the three key elements:
Problems solved by technology
Method used
Benefits of technology
Problems solved by technology
However, these reduction conditions either have certain dangers, such as explosive hydrogen; or the reagents are expensive, the reaction lacks atom economy, and more wastes need to be disposed of after the reaction, such as [(Ph 3 P)CuH] 6 (Stryker reagent), R 3 SiH, Hantzsch ester, etc.
Method used
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more
Image
Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
Click on the blue label to locate the original text in one second.
Reading with bidirectional positioning of images and text.
Smart Image
Examples
Experimental program
Comparison scheme
Effect test
Embodiment 1
[0025]
[0026] Under nitrogen protection, palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL), stirred at 25°C for 5 minutes, Add a solution of compound 1a (0.3 mmol) in DMA (0.5 mL), then react at 25°C for 2 hours, add saturated aqueous ammoniumchloride solution to stop the reaction, extract with ethyl acetate, combine the extracts, dry over sodium sulfate, and rotary evaporate Evaporated to dryness and purified by column chromatography, the product 3a was obtained with a yield of >99%. The mixture of enol and keto form, enol / keto = 16 / 84. 1 H NMR (400 MHz, CDCl 3 ): δ10.37 (br, 1H, enol), 7.78 (d, J = 7.6 Hz, 1H), 7.63 (t, J = 7.2 Hz, 1H),7.53-7.35 (m, 2H), 3.86 (s, 3H, enol), 3.79 (s, 3H, keto), 3.74 (dd, J = 8.1,3.9 Hz, 1H, keto), 3.57 (dd, J = 17.3, 3.4 Hz, 1H, keto), 3.52 (s, 2H, enol), 3.38 (dd, J = 17.2, 8.2 Hz, 1H, keto). 13 C NMR (151 MHz, CDCl 3 ): δ 199.58,169.68...
Embodiment 2
[0028]
[0029] Under nitrogen protection, palladium acetate (2.7 mg, 0.015 mmol, 5 mol%) and lithium hydride (7.2 mg, 0.9 mmol, 3.0 equiv) were suspended in DMF (1.5 mL), stirred at 25°C for 5 minutes, compound 1a (0.3 mmol ) in DMF (0.5mL), react at 100°C for 0.3 hours, add saturated aqueous ammoniumchloride solution to stop the reaction, extract with ethyl acetate, combine the extracts, dry with sodium sulfate, evaporate to dryness by rotary evaporation, column chromatography After purification, the product 3a was obtained in a yield of 91%.
Embodiment 3
[0031]
[0032] Under nitrogen protection, Pd 2 (dba) 3(2.7 mg, 0.003 mmol, 1 mol%) and potassium hydride (30% in oil, 200 mg, 1.5 mmol, 5 equiv) were suspended in THF (1.5 mL), stirred at 25°C for 5 minutes, and compound 1a (0.3mmol) was added solution in THF (0.5 mL), then react at 0°C for 10 hours, add saturated ammonium chlorideaqueous solution to stop the reaction, extract with ethyl acetate, combine the extracts, dry over sodium sulfate, evaporate to dryness by rotary evaporation, and purify by column chromatography , the product 3a was obtained in a yield of 82%.
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More
PUM
Login to View More
Abstract
The invention discloses a method for preparing a 1,3-dicarbonyl compound based on a metalhydride / palladiumcompound system. The method comprises the following steps: making a palladium compound and metalhydride suspend in a solvent under the protection of nitrogen; then adding an electron-deficient alkene compound for reacting at the temperature of 0 to 100 DEG C for 0.3 to 10 hours; the addinga saturated ammoniumchlorideaqueous solution for terminating the reaction; then performing extraction, drying by distillation and column chromatography purification to obtain a product of 1,3-dicarbonyl compound. The hydride and palladium compound catalysts used in the invention are readily-available reagents in a laboratory. Compared with the common hydrogen hydrogenating method, the method hasthe advantages of greater easiness in operation, higher security, mild conditions and high reaction yield.
Description
technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to the application of a metal hydride / palladium compoundsystem in the Michael-Dieckmann series reaction of electron-deficient alkenes, and in particular to the preparation of 1,3-dicarbonyl compounds based on a metal hydride / palladium compoundsystem method. Background technique [0002] Sodium hydride is a strong base that is often used in laboratories and industries. For a long time, there have been few reports about its use as a reducing agent. Existing technologies utilizing sodium hydride all require a large excess of sodium hydride (more than 5 equivalents), and require at least 2 equivalents of sodiumiodide as a promoter. [0003] The reduction of electron-deficient alkenes is a common chemical transformation to the corresponding saturated carbonyl compounds. This type of reaction is generally reduced using hydrogen / palladium carbon conditions; in add...
Claims
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More
Application Information
Patent Timeline
Application Date:The date an application was filed.
Publication Date:The date a patent or application was officially published.
First Publication Date:The earliest publication date of a patent with the same application number.
Issue Date:Publication date of the patent grant document.
PCT Entry Date:The Entry date of PCT National Phase.
Estimated Expiry Date:The statutory expiry date of a patent right according to the Patent Law, and it is the longest term of protection that the patent right can achieve without the termination of the patent right due to other reasons(Term extension factor has been taken into account ).
Invalid Date:Actual expiry date is based on effective date or publication date of legal transaction data of invalid patent.
Login to View More 
Login to View More