Chloroform → Ethyl 4-chloro-5-formyl-6,7-dihydro-3-methylthiobenzo[c]thiophene-1-carboxylate

HRID 1108353Notes

Reaction equation

HRID 1108353 reaction equation
[CH3:1][S:2][C:3]1[S:7][C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:5]2[CH2:13][CH2:14][CH2:15][C:16](=[O:17])[C:4]=12.P(Cl)(Cl)(Cl)=O.[CH:23]([Cl:26])(Cl)Cl>CN(C)C=O>[Cl:26][C:23]1[C:4]2[C:5](=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[S:7][C:3]=2[S:2][CH3:1])[CH2:13][CH2:14][C:15]=1[CH:16]=[O:17]

Participants

5

Reactant 3

HCID 6212ChloroformHCID 24813Phosphorus oxychlorideHCID 2778748Ethyl 3-(methylthio)-4-oxo-4,5,6,7-tetrahydrobenzo[c]thiophene-1-carboxylate

Product 1

HCID 2778781Ethyl 4-chloro-5-formyl-6,7-dihydro-3-methylthiobenzo[c]thiophene-1-carboxylateYield 73.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Ethyl 4,5,6,7-tetrahydro-3-methylthio-4-oxobenzo[c]thiophene-1-carboxylate (5.47 g) was dissolved in chloroform (130 ml) and added dropwise to a solution of phosphorus oxychloride (50.71 g) in N,N-dimethylformamide (40 ml) at 0° C. This mixture was stirred at room temperature, after which it was refluxed under heating in a nitrogen stream for 4.5 hours. The reaction mixture was poured over ice water and extracted with ethyl acetate. The organic layer was washed with water and dried (MgSO4), after which the solvent was distilled off to yield ethyl 4-chloro-5-formyl-6,7-dihydro-3-methylthiobenzo[c]thiophene-1-carboxylate (4.72 g, 73.8%), which was then recrystallized from ethyl acetate. Yellow prisms. Melting point 79-80° C.

Workup

  1. temperatureafter which it was refluxed
  2. temperatureunder heating in a nitrogen stream for 4.5 hours
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with water
  5. dry with materialdried (MgSO4)
  6. distillationafter which the solvent was distilled off

Sources & evidence

ORD record
ord-1fea6acf38b44a53ae5f09fd16aff76d
Source dataset
uspto-grants-2000_05
Patent number
US06066658

Reaction notes

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