Hydrogen Sulfide → HCID 69843250, compound

HRID 2120964Notes

Reaction equation

HRID 2120964 reaction equation
[C:1]([C:3]1[CH:32]=[CH:31][C:6]([C:7]([N:9]2[CH2:30][CH2:29][C:12]3([NH:16][C:15](=[O:17])[N:14]([CH2:18][CH2:19][CH2:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[C:13]3=[O:28])[CH2:11][CH2:10]2)=[O:8])=[CH:5][CH:4]=1)#[N:2].S.C([O-])(=O)C.[NH4+:38].C(=O)([O-])[O-].[K+].[K+].[CH3:45][C:46]([O:49][C:50]([O:52]C(OC(C)(C)C)=O)=O)([CH3:48])[CH3:47]>N1C=CC=CC=1.C(N(CC)CC)C.O>[C:46]([O:49][C:50]([NH:38][N:2]=[CH:1][C:3]1[CH:4]=[CH:5][C:6]([C:7]([N:9]2[CH2:30][CH2:29][C:12]3([NH:16][C:15](=[O:17])[N:14]([CH2:18][CH2:19][CH2:20][C:21]([O:23][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:22])[C:13]3=[O:28])[CH2:11][CH2:10]2)=[O:8])=[CH:31][CH:32]=1)=[O:52])([CH3:48])([CH3:47])[CH3:45]

Participants

9

Reactant 5

HCID 402Hydrogen SulfideHCID 11430Potassium CarbonateHCID 90495Di-tert-butyl dicarbonateHCID 517165Ammonium AcetateHCID 23435736HCID 23435736, compound

Product 1

HCID 69843250HCID 69843250, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 8471TriethylamineSolvent

Procedure

A solution of 0.9 g (2.0 mmol) of the compound from Step C in a mixture of 13 ml dry pyridine and 1.8 ml triethylamine was saturated with hydrogen sulfide during 2 h. After stirring over night at room temperature it was poured into water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure followed by solution in 100 ml toluene. The solvent was evaporated in vacuo again, in order to remove remaining traces of pyridine. The residue was dissolved in 5 ml acetone, treated with 5 ml iodomethane, and heated with reflux for 75 minutes. It was concentrated to dryness, dissolved in 5 ml methanol, treated with 0.3 g (3.9 mmol) ammonium acetate, and heated for 2 h at 60° C. The solvent was removed in vacuo, and the solid residue was washed by stirring with ether, dissolved in 20 ml of a mixture of THF/water 1:1 followed by, addition of 1.8 g (13.0 mmol) potassium carbonate and 2.0 g (9.2 mmol) Boc2O. After stirring over night at room temperature it was diluted with water, extracted with ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. The title compound was obtained from the residue by chromatography on silica gel with dichloromethane/ethanol 9:1.

Workup

  1. extractionextracted three times with ethyl acetate
  2. dry with materialThe combined organic layers were dried over sodium sulfate
  3. concentrationconcentrated under reduced pressure
  4. customThe solvent was evaporated in vacuo again
  5. customin order to remove
  6. dissolutionThe residue was dissolved in 5 ml acetone
  7. additiontreated with 5 ml iodomethane
  8. temperatureheated
  9. temperaturewith reflux for 75 minutes
  10. concentrationIt was concentrated to dryness
  11. dissolutiondissolved in 5 ml methanol
  12. temperatureheated for 2 h at 60° C
  13. customThe solvent was removed in vacuo
  14. washthe solid residue was washed
  15. stirringby stirring with ether
  16. dissolutiondissolved in 20 ml of a mixture of THF/water 1:1
  17. stirringAfter stirring over night at room temperature it
  18. extractionextracted with ethyl acetate
  19. dry with materialthe organic layer was dried over sodium sulfate
  20. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-1f1f09d1fc81414cb2d34267a0712e2c
Source dataset
uspto-grants-2004_02
Patent number
US06693109B2

Reaction notes

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