Bromine → HCID 13784978, compound

HRID 329446Notes

Reaction equation

HRID 329446 reaction equation
[C:1]([C:5]1[CH:6]=[CH:7][C:8]([S:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[C:9]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:10]=1)(=O)[CH2:2]C.[CH:23]([O-])([O-:26])[O:24][CH3:25].[Cl-].[Cl-].[Cl-].[Cl-].C=C.BrBr>[Br-].[Zn+2].[Br-].C(Cl)Cl.O.CO>[CH3:25][O:24][C:23]([CH:1]([C:5]1[CH:6]=[CH:7][C:8]([S:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)=[C:9]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:10]=1)[CH3:2])=[O:26]

Participants

9

Reactant 4

HCID 24408BromineHCID 14279620Methyl [2-(phenylsulfanyl)-5-propanoylphenyl]acetateHCID 18364422HCID 18364422, compoundHCID 53629101Methylorthoformate

Product 1

HCID 13784978HCID 13784978, compoundYield 80%

Reagents, catalysts & solvents 4

HCID 10421208Zinc bromideCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred mixture of 15.72 g (50 mmol.) of methyl 5-propionyl-2-phenylthiophenylacetate, 13.32 g (125.5 mmol.) of methyl orthoformate, 20 ml of methanol and 20 ml ethylene tetrachloride was dropwise added under stirring 8.39 g (52.5 mmol.) of bromine for a period of 30 minutes. The resulting mixture was further stirred at room temperature for 30 minutes, and then was heated slowly to 110° C. for 1 hour, under distilling off materials having a low boiling point. To the reaction mixture was added 0.90 g (4.0 mmol.) of zinc bromide, and the mixture was heated to 110° C. under reflux for 3 hours. The reaction mixture was cooled, and 75 ml of water and 40 ml of methylene chloride were added. The organic layer was separated and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain 13.78 g of the desired product as a yellow oil (yield 80%, b.p. 212°-215° C./2 mmHg).

Workup

  1. additionwas dropwise added
  2. temperaturewas heated slowly to 110° C. for 1 hour
  3. distillationunder distilling off materials
  4. temperaturethe mixture was heated to 110° C.
  5. temperatureunder reflux for 3 hours
  6. temperatureThe reaction mixture was cooled
  7. customThe organic layer was separated
  8. distillationthe solvent was distilled off under reduced pressure
  9. distillationThe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-1b8d2aa8c20148fcb22f0bbd3a5d56f5
Source dataset
uspto-grants-1990_01
Patent number
US04891433

Reaction notes

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