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

HRID 751427Notes

Reaction equation

HRID 751427 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-f1dc3f98751b43f4be5ac6cbc431d2a4
Source dataset
uspto-grants-2008_07
Patent number
US07405306B2

Reaction notes

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