Oxalyl chloride → HCID 10684134, compound

HRID 466971Notes

Reaction equation

HRID 466971 reaction equation
C(Cl)(=O)C(Cl)=O.[C:7]([CH2:10][S:11][CH:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]2[O:24][CH2:25][O:26][C:20]=2[CH:19]=1)[C:13]([O:15][CH3:16])=[O:14])(O)=[O:8]>CN(C=O)C.O1CCCC1>[CH2:25]1[O:26][C:20]2[C:21](=[CH:22][C:23]3[C:7](=[O:8])[CH2:10][S:11][CH:12]([C:13]([O:15][CH3:16])=[O:14])[CH2:17][C:18]=3[CH:19]=2)[O:24]1

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 10661787HCID 10661787, compound

Product 1

HCID 10684134HCID 10684134, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Oxalyl chloride (14.8 g) and DMF (3 drops) were successively added dropwise to a solution of methyl 2-carboxymethylthio-3-(3,4-methylenedioxyphenyl)propionate (29.0 g) in tetrahydrofuran (THF) (200 ml), followed by stirring for 1.5 hours at room temperature and concentrated under reduced pressure. The residual oil was dissolved in dichloromethane (250 ml). To the solution was added dropwise tin(IV) chloride (SnCl4)(55.6 g) under ice-cooling. The mixture was stirred for an hour under ice-cooing, to which 2NHCl (100 ml) was added dropwise. The dichloromethane layer was separated, washed with water, dried (MgSO4) and distilled off the solvent to give crystals of methyl 7,8-methylenedioxy-5-oxo-1,2,4,5-tetrahydro-3-benzothiepine-2-carboxylate (17.0 g, 63%). Recrystallization from ethyl acetate gave colorless prisms.

Workup

  1. concentrationconcentrated under reduced pressure
  2. dissolutionThe residual oil was dissolved in dichloromethane (250 ml)
  3. additionTo the solution was added dropwise tin(IV) chloride (SnCl4)(55.6 g) under ice-
  4. temperaturecooling
  5. stirringThe mixture was stirred for an hour under ice-cooing
  6. additionto which 2NHCl (100 ml) was added dropwise
  7. customThe dichloromethane layer was separated
  8. washwashed with water
  9. dry with materialdried (MgSO4)
  10. distillationdistilled off the solvent

Sources & evidence

ORD record
ord-f10584b56acf43748d412d49d2dee6b3
Source dataset
uspto-grants-1992_10
Patent number
US05158943

Reaction notes

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