Sodium Chloride → HCID 22620493, compound

HRID 840970Notes

Reaction equation

HRID 840970 reaction equation
[O:1]=[C:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][CH2:5][CH2:4][CH:3]1[C:13]([O:15][CH2:16][CH3:17])=[O:14].[O-][CH2:19]C.[K+].C1(C)C=CC(S(OC)(=O)=O)=CC=1.[Cl-].[Na+].[BH4-].[Na+].[Cl-].[NH4+]>C1(C)C=CC=CC=1>[CH3:19][O:1][C:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][CH2:5][CH2:4][C:3]=1[C:13]([O:15][CH2:16][CH3:17])=[O:14]

Participants

8

Reactant 6

HCID 5234Sodium ChlorideHCID 6645Methyl p-toluenesulfonateHCID 25517Ammonium ChlorideHCID 4311764Sodium borohydrideHCID 10331497Ethyl 6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptene-6-carboxylateHCID 23670592Potassium ethoxide

Product 1

HCID 22620493HCID 22620493, compoundYield 52.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of ethyl 6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptene-6-carboxylate (12.0 g, 51.7 mmol), potassium ethoxide (4.78 g, 56.8 mmol) and toluene (200 ml) was stirred at room temperature for 0.5 hour and then distilled under reduced pressure to remove the solvent. The residue was dissolved in N-methylpyrrolidinone (150 ml), followed by adding thereto methyl p-toluenesulfonate (10.6 g, 56.8 mmol), and the resulting mixture was stirred at 55-60° C. for 1 hour. The reaction mixture was poured into a cold aqueous sodium chloride solution and extracted twice with ethyl acetate, and the extract solution was washed twice with a 5% aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was dissolved in ethanol. The resulting solution was cooled to 0° C., followed by adding thereto sodium tetrahydroborate (0.98 g, 25.8 nmol), and the resulting mixture was stirred at 0° C. for 1.5 hours. The reaction mixture was poured into a cold aqueous ammonium chloride solution and extracted twice with ethyl acetate, and the extract solution was washed twice with a 5% aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was purified by a silica gel column chromatography (eluent: ethyl acetate/n-hexane=2/98) to obtain 6.66 g of ethyl 9-methoxy-6,7-dihydro-5H-benzocycloheptene-8-carboxylate.

Workup

  1. distillationdistilled under reduced pressure
  2. customto remove the solvent
  3. dissolutionThe residue was dissolved in N-methylpyrrolidinone (150 ml)
  4. additionby adding
  5. extractionextracted twice with ethyl acetate
  6. washthe extract solution was washed twice with a 5% aqueous sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationThe solvent was distilled off under reduced pressure
  9. dissolutionthe resulting residue was dissolved in ethanol
  10. temperatureThe resulting solution was cooled to 0° C.
  11. additionby adding
  12. extractionextracted twice with ethyl acetate
  13. washthe extract solution was washed twice with a 5% aqueous sodium chloride solution
  14. dry with materialdried over anhydrous magnesium sulfate
  15. distillationThe solvent was distilled off under reduced pressure
  16. customthe resulting residue was purified by a silica gel column chromatography (eluent: ethyl acetate/n-hexane=2/98)

Sources & evidence

ORD record
ord-22ae835b9e1c4d61afb2fecdb3bd3240
Source dataset
uspto-grants-2002_04
Patent number
US06369110B1

Reaction notes

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