Stannous Chloride → (S)-N-((3-(3-fluoro-4-hydrazinophenyl)-2-oxooxazolidin-5-yl)methyl)acetamide

HRID 1844497Notes

Reaction equation

HRID 1844497 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:12][C@H:11]([CH2:13][NH:14][C:15](=[O:17])[CH3:16])[O:10][C:9]2=[O:18])=[CH:4][C:3]=1[F:19].[N:20]([O-])=O.[Na+].Cl[Sn]Cl>CO.O.Cl>[F:19][C:3]1[CH:4]=[C:5]([N:8]2[CH2:12][C@H:11]([CH2:13][NH:14][C:15](=[O:17])[CH3:16])[O:10][C:9]2=[O:18])[CH:6]=[CH:7][C:2]=1[NH:1][NH2:20]

Participants

7

Reactant 3

HCID 24479Stannous Chloride2×HCID 10778218(S)-N-[3-[3-Fluoro-4-aminophenyl]-2-oxo-5-oxazolidinyl]methylacetamideHCID 23668193Sodium Nitrite

Product 1

HCID 10731576(S)-N-((3-(3-fluoro-4-hydrazinophenyl)-2-oxooxazolidin-5-yl)methyl)acetamideYield 70%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolvent3×HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

3 g (11.22 mmol) of (S)—N-((3-(4-amino-3-fluorophenyl)-2-oxooxazolidin-5-yl) methyl)acetamide (7) was dissolved in a blend of 6 mL methanol, 12 mL water and 3 mL concentrated hydrochloric acid. The resultant mixture was stirred for 10 minutes in an ice-salt bath to maintain the internal temperature below −5° C. Then, a NaNO2 solution prepared in advance was slowly dropped into the mixture. After completion of the addition, the mixture was stirred in the ice-salt bath for another 30 minutes to prepare a reaction solution of diazonium salt. Meanwhile, 6.08 g of SnCl2 was dissolved in a concentrated hydrochloric acid under vigorous stirring in an ice-salt bath. The reaction solution of diazonium salt prepared above was slowly dropped into the SnCl2 solution in hydrochloric acid, and then the mixture was warmed naturally to room temperature and stirred for another 2 hours. After completion of the reaction, the reactant was buffered to a pH between 7 and 8 with 1 ON NaOH solution. After the solvent was evaporated in a rotary evaporator, the resultant material was repeatedly grinded with methanol. After the solvent methanol was rotary evaporated, the residue was recrystallized with ethanol and then filtered to afford a light yellow crystalline solid weighed 2.2 g, with a yield of 70%. The product was kept under low temperature and in a dry place.

Workup

  1. temperatureto maintain the internal temperature below −5° C
  2. additionwas slowly dropped into the mixture
  3. additionAfter completion of the addition
  4. stirringstirred for another 2 hours
  5. customAfter completion of the reaction
  6. customAfter the solvent was evaporated in a rotary evaporator
  7. customthe resultant material was repeatedly grinded with methanol
  8. customthe residue was recrystallized with ethanol
  9. filtrationfiltered
  10. customto afford a light yellow crystalline solid

Sources & evidence

ORD record
ord-6a6742763c0d4618a5a522deb829bd41
Source dataset
uspto-grants-2015_02
Patent number
US08946436B2

Reaction notes

Loading…