3,5-Heptanedione

Clear colorless liquid

60g NaH (50percent) was suspended in 200mL of anhydrous benzene, heated and stirred at reflux for 30 minutes, cooled to 60°C, and 2mL of ethanol was added dropwise. The 2.5mol ethyl propionate and 1.0mol butanone mixture was slowly added dropwise to the reaction flask, after the addition reaction for 2 hours. Then cooled to room temperature, under the protection of N 2 was added dropwise 200mL of water, with dilute hydrochloric acid to adjust the PH value of 7.0, the reaction liquid was statically layered, the organic layer was separated, and 50 mL of acetic acid was added to treat the organic layer. The solvent was recovered and the crude 3, 5-heptanedione was distilled off under reduced pressure. The crude 3, 5-heptanedione was dissolved in 200 ml of ethanol. 355 g of a cupric chloride solution of 55 g of cupric chloride in 300 g of water was added to form a chelate with 3, 5-heptanedione and filtered to obtain a sapphire 3, 5-heptanedione copper salt chelate. The chelate was dissolved in 1000 mL of 20percent sulfuric acid and extracted three times with 500 mL of methylene chloride. The organic layer was dried over anhydrous sodium sulfide, and methylene chloride was recovered to obtain 65.3 g of the product 3, 5-heptanedione (boiling point: 174-175°C) with a content of 97.3percent. (Measured by gas chromatography), a yield of 49.6percent (butanone as a reference).60g NaH (50percent) was suspended in 200mL of anhydrous benzene, heated with stirring and refluxed for 30 minutes, cooled to 60 °C, 2mL ethanol was added dropwise, a mixture of 2.5mol ethyl propionate and 1.0mol butanone slowly It was added dropwise to the reaction flask. After the addition, the reaction was carried out for 2 hours. Then it was cooled to room temperature, and 200 mL of water was added dropwise under N2 protection. The pH was adjusted to 7.0 with dilute hydrochloric acid. The reaction was allowed to stand for stratification, and the organic layer was separated. The organic layer was treated with 50 mL of acetic acid, and the solvent was recovered and distilled under reduced pressure. 3 , 5-Heptanedione crude product, the crude product of 3, 5-heptanedione was dissolved in 200 ml of ethanol, and 355 g of a copper chloride solution of 55 g of copper chloride in 300 g of water was added to form with 3, 5-heptanedione. Compounds were filtered to give azure blue salt hydrates of 3, 5-heptanedione. The chelate was dissolved in 20percent dilute sulfuric acid (1000 mL) and extracted three times with 500 mL of dichloromethane. The organic layer was dried over anhydrous sodium sulfide and dichloromethane was recovered to give the product 3, 5-heptanedione 65.3 g (boiling point: 174). -175°C), content 97.3percent (measured by gas chromatography), yield 49.6percent (on methyl ethyl ketone basis).In a three-necked flask, 11.2 g of potassium tert-butoxide (0.1 mol) was added to 50 mL of anhydrous methyl tert-butyl ether, and the mixture was heated to reflux for 30 minutes and cooled to 35°C. 0.3 mol of methyl propionate and 0.1 mol of methyl ethyl ketone were slowly added dropwise to the reaction flask, and the reaction was continued for 2 hours after the addition was completed. Then, after cooling down to room temperature, 30 mL of water was added dropwise under N 2 protection. The pH was neutral with dilute hydrochloric acid. The reaction liquid was allowed to stand and stratify, and the organic layer was separated. The organic layer was analyzed by gas chromatography. The product 3, 5-heptanedione gave a reaction yield of 72.4percent (based on butanone).In a three-necked flask, 11.2 g of potassium t-butoxide (0.1 mol) was added to 50 mL of anhydrous methyl tert-butyl ether.Heat and stir for 30 minutes, and cool down to 35 °C.0.3 mol of methyl propionate and 0.1 mol of butanone were slowly added dropwise to the reaction flask.The reaction was carried out for 2 hours after the addition. Then cool down to room temperature, Under the protection of N 2 , 30 mL of water was added dropwise, the pH value was adjusted with dilute hydrochloric acid, and the reaction solution was allowed to stand for stratification.The organic layer was separated, and the organic layer was analyzed by gas chromatography to show thatThe reaction yield of the product 3, 5-heptanedione was 72.4percent (based on methyl ethyl ketone).In a 1-liter four-necked flask was added 135g (1.2mol) potassium tert-butoxide (purchased from Sinopharm Chemical Reagent Co., Ltd., referred to as 'Sinopharm'The same below) and 104.5g (1.16mol) of ethylene glycol dimethyl ether (purchased from Sinopharm)The mixture was heated to 20 ° C with heating under reflux with a mechanical stirrer.then, Constant pressure dropping funnel by constant addition of 319g (3.6mol)Methyl propionate(Purchased from Japan TCI company) and86.5 g (1.2 mol)Butanone(Purchased from Sinopharm) composition of the liquid mixture, The dropwise addition time was 20 min, then stirred at 75 ° C for another 4.5 hours, The temperature was lowered to 40 ° C, 120 g of ice water was added, and the pH was adjusted to 6 with concentrated hydrochloric acid.Then filtered with a suction filter, remove the potassium chloride, the filtrate was separated, the organic layer and the water layer separated.By gas chromatography analysis of the organic layer, 103 g (0.80 mol) was generated3, 5-heptanedioneThe yield was 66.6percent (based on butanone).

Enantioselective conjugate addition of 1,3-dicarbonyls to nitroolefins via nickel (II)-diamine catalysis.1

Molecular Weight:128.17
XLogP3:0.7
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:4
Exact Mass:128.083729621
Monoisotopic Mass:128.083729621
Topological Polar Surface Area:34.1
Heavy Atom Count:9
Complexity:102
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes