Diethyl Ether → HCID 10635346, compound

HRID 466973Notes

Reaction equation

HRID 466973 reaction equation
S(Cl)(Cl)=O.[C:5]([CH:8]([S:10][CH:11]([CH2:16][C:17]1[CH:22]=[CH:21][C:20]2OCO[C:19]=2[CH:18]=1)[C:12]([O:14][CH3:15])=[O:13])[CH3:9])([OH:7])=O.[CH3:26]COCC>N1C=CC=CC=1>[CH3:9][C@@H:8]1[S:10][C@@H:11]([C:12]([O:14][CH3:15])=[O:13])[CH2:16][C:17]2[CH:18]=[CH:19][C:20]([CH3:26])=[CH:21][C:22]=2[C:5]1=[O:7]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 24386Thionyl ChlorideHCID 10519166HCID 10519166, compound

Product 1

HCID 10635346HCID 10635346, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 1049PyridineCatalyst

Procedure

Thionyl chloride (16.4 g) and pyridine (3 drops) were successively added dropwise to a solution of methyl 2-(1-carboxyethyl)thio-3-(3,4-methylenedioxyphenyl)propionate (26.0 g) in ether (250 ml), followed by stirring for an hour at room temperature and for an hour under reflux. The mixture was concentrated under reduced pressure. The residual oil was dissolved in dichloromethane (50 ml) and the resultant solution was added dropwise to a mixture of aluminum chloride (AlCl3)(27.0 g) and dichloromethane (200 ml) under ice-cooling. After stirring for two hours under ice-cooling, the mixture was poured into ice-water. The dichloromethane layer was separated, washed with water, dried (MgSO4) and distilled to remove the solvent. The residual oil was dissolved in methanol (250 ml), to which a solution of sodium methoxide in methanol (28%, 10 ml) was added. The mixture was stirred for 1.5 hours at room temperature, to which 2N--HCl (250 ml) was added. The precipitated crystals was collected by filtration, affording methyl trans-4,7-dimethyl-5-oxo-1,2,4,5 -tetrahydro-3-benzothiepine-2-carboxylate (15.0 g, 62%). Recrystallization from ethyl acetate-hexane gave colorless prisms.

Workup

  1. temperatureunder reflux
  2. concentrationThe mixture was concentrated under reduced pressure
  3. dissolutionThe residual oil was dissolved in dichloromethane (50 ml)
  4. additionthe resultant solution was added dropwise to a mixture of aluminum chloride (AlCl3)(27.0 g) and dichloromethane (200 ml) under ice-
  5. temperaturecooling
  6. stirringAfter stirring for two hours under ice-
  7. temperaturecooling
  8. additionthe mixture was poured into ice-water
  9. customThe dichloromethane layer was separated
  10. washwashed with water
  11. dry with materialdried (MgSO4)
  12. distillationdistilled
  13. customto remove the solvent
  14. dissolutionThe residual oil was dissolved in methanol (250 ml), to which a solution of sodium methoxide in methanol (28%, 10 ml)
  15. additionwas added
  16. stirringThe mixture was stirred for 1.5 hours at room temperature, to which 2N
  17. additionHCl (250 ml) was added
  18. filtrationThe precipitated crystals was collected by filtration

Sources & evidence

ORD record
ord-cf244bd11cbd4ad59ae2f58322917187
Source dataset
uspto-grants-1992_10
Patent number
US05158943

Reaction notes

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