Water → HCID 70818481, compound

HRID 591070Notes

Reaction equation

HRID 591070 reaction equation
Cl[C:2](=[O:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[Cl-].[Al+3].[Cl-].[Cl-].[Br:13][C:14]1[CH:18]=[C:17]([CH3:19])[S:16][C:15]=1[Cl:20].O>ClCCl>[Br:13][C:14]1[C:18]([C:2](=[O:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4])=[C:17]([CH3:19])[S:16][C:15]=1[Cl:20]

Participants

6

Reactant 4

HCID 962WaterHCID 20884Ethoxalyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 20732074HCID 20732074, compound

Product 1

HCID 70818481HCID 70818481, compoundYield 57.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Under a nitrogen atmosphere, ethyl chlorooxoacetate (898 μL, 8.04 mmol) and aluminum chloride (III) (2.14 g, 16.07 mmol) were added successively at −10° C. to a solution of 3-bromo-2-chloro-5-methylthiophene (44a) (1.7 g, 8.04 mmol) in dichloromethane (84 mL). After 1 hour at 0° C., the mixture was stirred at room temperature for 8 hours. The reaction mixture was slowly hydrolyzed at 0° C. with water. The organic layer was separated, washed with hydrochloric acid 1 N, brine, dried over sodium sulfate, filtered, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 90/10) to give the desired keto-ester (44b) as an orange solid (1.44 g, 4.6 mmol, 56%).

Workup

  1. customThe organic layer was separated
  2. washwashed with hydrochloric acid 1 N, brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 90/10)

Sources & evidence

ORD record
ord-c9738038c355460fa53351e37df2f27e
Source dataset
uspto-grants-2016_01
Patent number
US09238026B2

Reaction notes

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