Diiodomethane → HCID 18182224, compound

HRID 1359412Notes

Reaction equation

HRID 1359412 reaction equation
N[C:2]1[S:6][C:5]2[CH2:7][CH:8]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:9][CH2:10][C:4]=2[C:3]=1[C:16](=[O:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.ICI.N(OCCC(C)C)=O.[BH4-].[Na+]>C(O)C.C(OCC)(=O)C.O1CCCC1>[OH:23][CH:16]([C:3]1[C:4]2[CH2:10][CH2:9][CH:8]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:7][C:5]=2[S:6][CH:2]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

8

Reactant 4

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 4311764Sodium borohydrideHCID 18182175HCID 18182175, compound

Product 1

HCID 18182224HCID 18182224, compoundYield 54.2%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 21.5 g of 2-amino-3-benzoyl-6-ethoxycarbonyl-4,5,6,7-tetrahydrobenzo[b]thiophene, 12.5 g of cuprous iodide, 26.3 ml of diiodomethane, 26.3 ml of isopentyl nitrite and 250 ml of tetrahydrofuran was heated under reflux for 1.5 hours. After cooling as it was, 500 ml of ethyl acetate was added to the reaction solution. The insoluble matters were filtered off, the mixture was subjected to silica gel column chromatography, and eluted with hexane and then with hexane/ethyl acetate (10:1), to give 17.4 g of a crude product. 1.5 g of sodium borohydride was added little by little to a solution of 200 ml of ethanol containing 17.4 g of this crude product under ice-cooling. After stirring at room temperature for one hour, the solvent was removed. Ethyl acetate and water were added to the residue, followed by extracting with ethyl acetate. The organic phase was washed with brine and the solvent was removed. The residue was subjected to silica gel column chromatography, and eluted with hexane and then with hexane/ethyl acetate (4:1), to give 11.2 g of the target compound.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 1.5 hours
  3. temperatureAfter cooling as it
  4. filtrationThe insoluble matters were filtered off
  5. washeluted with hexane
  6. customwith hexane/ethyl acetate (10:1), to give 17.4 g of a crude product
  7. temperaturecooling
  8. customthe solvent was removed
  9. additionEthyl acetate and water were added to the residue
  10. extractionby extracting with ethyl acetate
  11. washThe organic phase was washed with brine
  12. customthe solvent was removed
  13. washeluted with hexane

Sources & evidence

ORD record
ord-1e0197eb128d437dbe1dd3030b6364ba
Source dataset
uspto-grants-2003_07
Patent number
US06599917B1

Reaction notes

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