Ethyl 3-chloro-3-oxopropionate → HCID 21114499, compound

HRID 2252715Notes

Reaction equation

HRID 2252715 reaction equation
Cl[C:2](=[O:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[Cl:10][C:11]1[CH:19]=[C:18]2[C:14]([CH:15]=[C:16]([C:21]([O:23][CH3:24])=[O:22])[N:17]2[CH3:20])=[CH:13][CH:12]=1>ClCCCl.[Ti](Cl)(Cl)(Cl)Cl>[Cl:10][C:11]1[CH:19]=[C:18]2[C:14]([C:15]([C:2](=[O:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])=[C:16]([C:21]([O:23][CH3:24])=[O:22])[N:17]2[CH3:20])=[CH:13][CH:12]=1

Participants

5

Reactant 2

HCID 118931Ethyl 3-chloro-3-oxopropionateHCID 4777845HCID 4777845, compound

Product 1

HCID 21114499HCID 21114499, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 111,2-DichloroethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 6.2 ml (48.4 mmol) of ethyl 3-chloro-3-oxopropanoate in 70 ml of 1,2-dichloroethane is cooled to 0° C. In small portions 5.3 ml (48.3 mmol) of titanium tetrachloride are added and the mixture is stirred at 0° C. for 30 minutes. A solution of 4.3 g (19.2 mmol) of methyl 6-chloro-1-methyl-1H-indole-2-carboxylate in 35 ml of 1,2-dichloroethane is added and the mixture is stirred at ambient temperature for 12 h. It is poured into ice water and extracted with dichloromethane. The organic phase is separated off, washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue is purified by chromatography on a silica gel column (eluent: cyclohexane/ethyl acetate: 90/10 to 80/20). This gives a yellow solid, which is triturated in heptane and then in diisopropyl ether.

Workup

  1. stirringthe mixture is stirred at ambient temperature for 12 h
  2. extractionextracted with dichloromethane
  3. customThe organic phase is separated off
  4. washwashed with water
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue is purified by chromatography on a silica gel column (eluent: cyclohexane/ethyl acetate: 90/10 to 80/20)
  9. customThis gives a yellow solid, which
  10. customis triturated in heptane

Sources & evidence

ORD record
ord-826a76c5a67f461bac2965066dbdc73a
Source dataset
uspto-grants-2008_01
Patent number
US07323467B2

Reaction notes

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