Hydrazine hydrate (1:1) → HCID 12687102, compound

HRID 866926Notes

Reaction equation

HRID 866926 reaction equation
[C:1]([C:4]1[C:9]2[CH2:10][C:11](=O)[C:12]3[CH:18]=[CH:17][CH:16]=[C:15](F)[C:13]=3[S:14][C:8]=2[CH:7]=[CH:6][CH:5]=1)([OH:3])=[O:2].[OH2:21].NN>C(O)C.O1CCOCC1>[C:1]([C:4]1[C:9]2[CH2:10][CH2:11][C:12]3[CH:18]=[CH:17][CH:16]=[C:15]([OH:21])[C:13]=3[S:14][C:8]=2[CH:7]=[CH:6][CH:5]=1)([OH:3])=[O:2]

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 23337059HCID 23337059, compound

Product 1

HCID 12687102HCID 12687102, compoundYield 12.7%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 312751,4-DioxaneSolvent

Procedure

5.0g of 9-carboxy-4-fluoro-10,11-dihydrodibenzo[b,f]thiepin-11-one and 5.0g of 100% hydrazine hydrate were dissolved in the mixed solvent of 50ml of ethanol and 50ml of dioxane. The resulting mixture was heated under reflux for 5 hours. The solvent was evaporated under reduced pressure to obtain the residue, which was washed with ethanol. To this was added 5.0g of sodium hydroxide in 100ml of diethylene glycol and the resulting mixture was heated with stirring at 180°-200° C for 2 hours. After cooling, water was added to the mixture, which was extracted with benzene. The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated to obtain a glutinous residue which was chromatographed over silica gel, and eluted with benzene-ethyl acetate (1:1). Recrystallization of the thus obtained crude product from methanol-water afforded 600mg of 9-carboxy-4-hydroxy-10,11-dihydrodibenzo-[b,f]thiepin having a melting point of 171°-173° C.

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureunder reflux for 5 hours
  3. customThe solvent was evaporated under reduced pressure
  4. customto obtain the residue, which
  5. washwas washed with ethanol
  6. additionTo this was added 5.0g of sodium hydroxide in 100ml of diethylene glycol
  7. temperaturethe resulting mixture was heated
  8. temperatureAfter cooling
  9. additionwater was added to the mixture, which
  10. extractionwas extracted with benzene
  11. extractionextracted with ethyl acetate
  12. washThe extract was washed with water
  13. dry with materialdried over anhydrous sodium sulfate
  14. customThe solvent was evaporated
  15. customto obtain a glutinous residue which
  16. customwas chromatographed over silica gel
  17. washeluted with benzene-ethyl acetate (1:1)
  18. customRecrystallization of the
  19. customthus obtained crude product from methanol-water

Sources & evidence

ORD record
ord-5486fdb13d6e4c40bec0f4aa23e4e7d9
Source dataset
uspto-grants-1978_07
Patent number
US04101667

Reaction notes

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