Ethyl 2-chloro-β-oxobenzenepropanoate

Experimental operation: Take malonate potassium salt 1.00g (about 5.47mmol) and anhydrous magnesium chloride was added 0.65g (about 6.84mmol) in 25mL round bottom flask, 0.55g triethylamine was dropped after 6mL dissolved in acetonitrile, stirred at room temperature for 30min. Then dropped by 2mL acetonitrile dissolved 0.48g (2.5mmol) of o-chlorobenzoyl chloride 1c, supplemented triethylamine 0.06mL, stirred at room temperature overnight. Post-treatment: 30mL of water was added to dilute the reaction solution, and then were added 30, 20, 20mL ethyl acetate and the ethyl acetate layer was collected. After washing with saturated brine 30mL ethyl acetate layer was dried over anhydrous sodium sulfate, and spin dry column chromatography (PE: EA = 15: 1) 2c product obtained is isolated, a yield of 91percentExperimental operation: Take malonate potassium salt 1.00 g (about5.47 mmol) and anhydrous magnesium chloride 0.65 g (about 6.84mmol) in 25 mLround bottom flask, 0.55 g of triethylamine was added dropwise after 6 mL ofacetonitrile was dissolved, followed by stirring at room temperature for 30min. Then dropped by 2 mL of acetonitrile was dissolved 0.48 g (2.5 mmol) ofo-chlorobenzoyl chloride 1c, supplemented triethylamine 0.06 mL, stirred atroom temperature overnight. After treatment: 30 mL of water was added to dilutethe reaction solution, and then were added 30, 20, 20 mL ethyl acetate, and theethyl acetate layer was collected. After, 30 mL with saturated brine ethylacetate layer was dried over anhydrous sodium sulfate, and spin dry columnchromatography (PE: EA = 15: 1) to give the product isolated 2c, in 91percent yield.A. Ethyl 3-(2-chlorophenyl)-3-oxopropanoate [00192] Sodium hydride (1.45 g, 36 mmol) and diethyl carbonate (2.14 g, 18 mmol) were suspended in 10 ml of THF. l-(2-Chlorophenyl)ethanone (1.4 g, 9 mmol) was gradually added into the reaction flask, maintaining the reaction mixture temperature at 40 °C for 2 h. Then 1 mL of ethanol was added thereto and heated under reflux conditions for 4 h. After cooling, 1 mL of ethanol was added and the mixture was poured onto ice water, and extracted with ether. Ether extracts are combined, washed with water, dried with anhydrous magnesium sulfate, and evaporated. The resulting oil is purified by flash column chromatography (PE/EA = 50/1) to afford the title compound (680 mg, 34percent) as a yellow oil. 1H NMR (400 MHz, CDC1EXAMPLE 5 EXAMPLE 5 Application of chiral spiro-pyridylamidophosphine ligand (R)-Ii (prepared in Example 9) in the asymmetric catalytic hydrogenation reaction of carbonyl compounds[0059] [0060] Under the protection of nitrogen atmosphere, 0.5 mg (0.74mumol) [Ir(COD)]Cl2, 1.2 mg (1.6mumol) (R)-Ii were added to the inner hydrogenation tube. Subsequently, 1 ml absolute ethyl alcohol was added and stirred for 1 h at room temperature. The inner reaction tube was placed into the hydrogenation reactor. After substitution by hydrogen, the reaction was stirred for 1 h at a hydrogen pressure of 1 atmosphere. The reactor was opened, and 7.5-150 mmol substrate (solid substrate, added after dissolved by ethanol) was added, followed by 0.05-25 mmol potassium tert-butoxide solution in ethanol (0.5 ml (0.1 mmol/mL)-25 ml (1 mmol/mL)) added with a syringe. The reactor was sealed, and hydrogen was filled to a pressure of 8-10 atm, and the reaction was stirred under the hydrogen pressure at room temperature for a while ranging from 10 minutes to 24 hours. After the hydrogenation was finished, the reaction solution was filtered through a short silica gel column to remove the catalyst, and the conversion rate and yield of the reaction were analyzed by gas chromatography or nuclear magnetic resonance (NMR); and the optical purity of the product was analyzed by gas chromatography or high performance liquid chromatography. The results of the hydrogenation experiments were listed in Table 1.Application of Chiral Spiro-Pyridylamidophosphine Ligand (R)-Ii (Prepared in Example 9) in the Asymmetric Catalytic Hydrogenation Reaction of Carbonyl Compounds Under the protection of nitrogen atmosphere, 0.5 mg (0.74 gmol) [Ir(COD)]Cl2, 1.2 mg (1.6 mumol) (R)-Ii were added to the inner hydrogenation tube. Subsequently, 1 ml absolute ethyl alcohol was added and stirred for 1 h at room temperature. The inner reaction tube was placed into the hydrogenation reactor. After substitution by hydrogen, the reaction was stirred for 1 h at a hydrogen pressure of 1 atmosphere. The reactor was opened, and 7.5-150 mmol substrate (solid substrate, added after dissolved by ethanol) was added, followed by 0.05-25 mmol potassium tert-butoxide solution in ethanol (0.5 ml (0.1 mmol/mL)-25 ml (1 mmol/mL)) added with a syringe. The reactor was sealed, and hydrogen was filled to a pressure of 8-10 atm, and the reaction was stirred under the hydrogen pressure at room temperature for a while ranging from 10 minutes to 24 hours. After the hydrogenation was finished, the reaction solution was filtered through a short silica gel column to remove the catalyst, and the conversion rate and yield of the reaction were analyzed by gas chromatography or nuclear magnetic resonance (NMR); and the optical purity of the product was analyzed by gas chromatography or high performance liquid chromatography. The results of the hydrogenation experiments were listed in Table 1.

Molecular Weight:226.65
XLogP3:2.5
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:5
Exact Mass:226.0396719
Monoisotopic Mass:226.0396719
Topological Polar Surface Area:43.4
Heavy Atom Count:15
Complexity:240
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes