Hydrochloric Acid → Ethyl 4-chloro-3-oxopentanoate

HRID 993454Notes

Reaction equation

HRID 993454 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([O-:5])=O.[K+].[Cl-].[Mg+2].[Cl-].C(N(CC)CC)C.[Cl:21][CH:22](C)[C:23](Cl)=O.Cl>C(#N)C.[Ti]>[Cl:21][CH:22]([CH3:23])[C:3](=[O:5])[CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 1110192-Chloropropionyl chlorideHCID 3446434Potassium ethyl malonateHCID 5360315Magnesium Chloride

Product 1

HCID 13030833Ethyl 4-chloro-3-oxopentanoateYield 58%

Reagents, catalysts & solvents 2

HCID 23963TitaniumCatalystHCID 6342AcetonitrileSolvent

Procedure

Potassium ethyl malonate, 34 g (200 mmole) (Organic Synthesis Coll. Vol. IV, p. 417), 23.75 g (250 mmole) magnesium chloride, and 44.5 ml (320 mmole) triethylamine were suspended in 1.0 L acetonitrile, with stirring, under nitrogen. 2-Chloro-propionyl chloride, 9.7 ml (100 mmole), was added and the mixture was stirred under nitrogen for 18 hours. 100 ml of 5N hydrochloric acid, was added and the reaction was stirred for 2 hours. Layers were separated and organics stripped to give 21.09 g of crude product which was filtered through 300 ml silica, eluting with 20% ethyl acetate/hexane to give 10.37 g (58%) product.

Workup

  1. stirringthe mixture was stirred under nitrogen for 18 hours
  2. stirringthe reaction was stirred for 2 hours
  3. customLayers were separated
  4. customto give 21.09 g of crude product which
  5. filtrationwas filtered through 300 ml silica
  6. washeluting with 20% ethyl acetate/hexane

Sources & evidence

ORD record
ord-5ce3e4f34cec4bc4b4b5afc2e48335d7
Source dataset
uspto-grants-2002_10
Patent number
US06472387B1

Reaction notes

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