Oxalyl chloride → HCID 10613711, compound

HRID 466972Notes

Reaction equation

HRID 466972 reaction equation
C(Cl)(=O)C(Cl)=O.[C:7]([CH:10]([S:12][CH:13]([CH2:18][C:19]1[CH:24]=[CH:23][C:22]2[O:25][CH2:26][O:27][C:21]=2[CH:20]=1)[C:14]([O:16][CH3:17])=[O:15])[CH3:11])([OH:9])=O>CN(C=O)C.O1CCCC1>[CH2:26]1[O:27][C:21]2[C:22](=[CH:23][C:24]3[C:7](=[O:9])[C@H:10]([CH3:11])[S:12][C@@H:13]([C:14]([O:16][CH3:17])=[O:15])[CH2:18][C:19]=3[CH:20]=2)[O:25]1

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 10519166HCID 10519166, compound

Product 1

HCID 10613711HCID 10613711, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Oxalyl chloride (13.6 g) and DMF (3 drops) were successively added dropwise to a solution of methyl 2-(1-carboxyethyl)thio-3-(3,4-methylenedioxyphenyl)propionate (27.8 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) tetrachloride (SnCl4)(51.0 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. The residual oil was dissolved in methanol (250 ml), to which a solution of sodium methoxide in methanol (28%, 10 ml) was added. The resultant solution was stirred for 1.5 hours at room temperature to which 2N--HCl (250 ml) was added. The precipitated crystals were collected by filtration to give methyl trans-7,8-methylenedioxy-4-methyl-5-oxo-1,2,4,5-tetrahydro-3-benzothiepine-2-carboxylate (19.0 g, 73%). 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) tetrachloride (SnCl4)(51.0 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
  11. dissolutionThe residual oil was dissolved in methanol (250 ml), to which a solution of sodium methoxide in methanol (28%, 10 ml)
  12. additionwas added
  13. stirringThe resultant solution was stirred for 1.5 hours at room temperature to which 2N
  14. additionHCl (250 ml) was added
  15. filtrationThe precipitated crystals were collected by filtration

Sources & evidence

ORD record
ord-b3ee258499cd45809ba0670080ccc9cc
Source dataset
uspto-grants-1992_10
Patent number
US05158943

Reaction notes

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