Ammonium Chloride → HCID 86653809, compound

HRID 243749Notes

Reaction equation

HRID 243749 reaction equation
Br[CH:2]1[CH2:4][CH2:3]1.[Mg].[O:6]=[C:7]1[C:16]2[CH:17]=[C:18]([CH2:21][C:22]([O:24][CH3:25])=[O:23])[CH:19]=[CH:20][C:15]=2[O:14][CH2:13][C:12]2[CH:11]=[CH:10][S:9][C:8]1=2.[Cl-].[NH4+]>C1COCC1>[CH:2]1([C:7]2([OH:6])[C:16]3[CH:17]=[C:18]([CH2:21][C:22]([O:24][CH3:25])=[O:23])[CH:19]=[CH:20][C:15]=3[O:14][CH2:13][C:12]3[CH:11]=[CH:10][S:9][C:8]2=3)[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 78037BromocyclopropaneHCID 5462224MagnesiumHCID 13051081Methyl 4,10-dihydro-10-oxothieno[3,2-c][1]benzoxepin-8-acetate

Product 1

HCID 86653809HCID 86653809, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

An anhydrous THF (50 mL) solution of bromocyclopropane (8.3 mL) was added dropwise to a metal magnesium (2.5 g), while heating. After the termination of dropwise addition, an anhydrous THF (20 mL) was added thereto, and the mixture was refluxed under heating for an additional 2 hours. Thereafter, the reaction mixture was allowed to air-cool, and this solution was added dropwise to an anhydrous THF (30 mL) solution of methyl (4-oxo-4,10-dihydro-9-oxa-3-thiabenzo[f]azulen-6-yl)acetate (10.0 g) previously chilled in an ice bath. After stirring the mixture for 30 minutes, an aqueous saturated ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with an aqueous saturated sodium chloride solution, and thereafter dried over anhydrous sodium sulfate. The solvents were distilled off under a reduced pressure, and the residue obtained was purified by silica gel column chromatography (hexane-ethyl acetate=5:1), to give 9.0 g (79%) of the captioned compound as an oily product.

Workup

  1. temperaturewhile heating
  2. additionAfter the termination of dropwise addition
  3. temperaturethe mixture was refluxed
  4. temperatureunder heating for an additional 2 hours
  5. temperatureto air-cool
  6. temperaturepreviously chilled in an ice bath
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe organic layer was washed with an aqueous saturated sodium chloride solution
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationThe solvents were distilled off under a reduced pressure
  11. customthe residue obtained
  12. customwas purified by silica gel column chromatography (hexane-ethyl acetate=5:1)

Sources & evidence

ORD record
ord-3aac4aea93524bc2a2e500c285891a92
Source dataset
uspto-grants-2014_02
Patent number
US08653285B2

Reaction notes

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