Hydrogen Sulfide → HCID 20464707, compound

HRID 325424Notes

Reaction equation

HRID 325424 reaction equation
[Cl:1][C:2]1[CH:24]=[CH:23][C:5]2[C:6](=[O:22])[C:7]3[N:8]([CH3:21])[C:9]([C:14](=O)[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:10][C:11]=3[CH2:12][S:13][C:4]=2[CH:3]=1.N1C=CN=C1.S>N1C=CC=CC=1>[Cl:1][C:2]1[CH:24]=[CH:23][C:5]2[C:6](=[O:22])[C:7]3[N:8]([CH3:21])[C:9]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:10][C:11]=3[CH2:12][S:13][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 402Hydrogen SulfideHCID 795ImidazoleHCID 20464729HCID 20464729, compound

Product 1

HCID 20464707HCID 20464707, compoundYield 90.7%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Ethyl 7-chloro-4,10-dihydro-10,α-dioxo-1-methyl-1H-[1]benzothiepino[4,3-b]pyrrole-2-acetate (87 mg, 0.23 mmol) is dissolved in pyridine (2 ml) and placed in a resealable pressure tube along with imidazole (100 mg) and a small stirring bar. The tube and its contents are cooled to -78° and hydrogen sulfide (0.5 ml) is conducted inside it. The tube is then sealed and allowed to come to room temperature with stirring. The mixture is stirred for three hours, then cooled again to -78° and the tube is opened. The tube is allowed to warm and the hydrogen sulfide evaporates. When bubbling ceases, the tube contents are poured into 1.2 N aqueous HCl (30 ml), and the resulting heterogeneous mixture is extracted with ether (2×50 ml). The combined ether layers are washed with 10% aqueous sodium carbonate (3×15 ml), saturated aqueous brine (15 ml), and dried with sodium sulfate. The solvent is removed to give a white solid smelling like garlic. This material is purified by preparative TLC (1/1 EtoAc/Hex, silica gel 0.70) to give 73 mg of ethyl 7-chloro-4,10-dihydro-1-methyl-10-oxo-1H-[1]benzothiepino[4,3-b]pyrrole-2-acetate (88%).

Workup

  1. temperatureThe tube and its contents are cooled to -78°
  2. customThe tube is then sealed
  3. customto come to room temperature
  4. stirringThe mixture is stirred for three hours
  5. temperaturecooled again to -78°
  6. temperatureto warm
  7. customthe hydrogen sulfide evaporates
  8. customWhen bubbling ceases
  9. additionthe tube contents are poured into 1.2 N aqueous HCl (30 ml)
  10. extractionthe resulting heterogeneous mixture is extracted with ether (2×50 ml)
  11. washThe combined ether layers are washed with 10% aqueous sodium carbonate (3×15 ml), saturated aqueous brine (15 ml)
  12. dry with materialdried with sodium sulfate
  13. customThe solvent is removed
  14. customto give a white solid smelling like garlic
  15. customThis material is purified by preparative TLC (1/1 EtoAc/Hex, silica gel 0.70)

Sources & evidence

ORD record
ord-3138525398a84d2e82772e25dc9b87c9
Source dataset
uspto-grants-1984_04
Patent number
US04440779

Reaction notes

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