Hydrazine → HCID 66521724, compound

HRID 537184Notes

Reaction equation

HRID 537184 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5](F)=[C:6]([CH:11]=1)[C:7](=S)[NH:8][CH3:9].[NH2:13][NH2:14]>CS(C)=O.C(OCC)(=O)C.[Cl-].[Na+].O>[Br:1][C:2]1[CH:11]=[C:6]2[C:5](=[CH:4][CH:3]=1)[NH:14][N:13]=[C:7]2[NH:8][CH3:9]

Participants

6

Reactant 2

HCID 9321HydrazineHCID 83390150HCID 83390150, compound

Product 1

HCID 66521724HCID 66521724, compoundYield 24%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 5-bromo-2-fluoro-N-methylbenzothioamide (480 mg, 1.9 mmol) and anhydrous hydrazine (0.61 mL, 19 mmol) in dimethylsulfoxide (6 mL) was heated to 80° C. and stirred for 1 hour. The temperature was increased to 100° C. and the reaction was stirred for 40 minutes. The temperature was increased further to 130° C. and the reaction was stirred for another 45 minutes. The reaction was cooled to room temperature and diluted with ethyl acetate and brine. The layers were separated and the aqueous was extracted with ethyl acetate (4×). The combined organics were washed with water and brine, dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography (20-70% ethyl acetate/heptanes) gave the title compound (103 mg, 23%) as a white solid. +ESI (M+H+1) 228.0; 1H NMR (400 MHz, CD3OD, δ): 7.78 (dd, J=1.85, 0.68 Hz, 1H), 7.29-7.40 (m, 1H), 7.17 (dd, J=8.88, 0.68 Hz, 1H), 2.94 (s, 3H).

Workup

  1. temperatureThe temperature was increased to 100° C.
  2. stirringthe reaction was stirred for 40 minutes
  3. temperatureThe temperature was increased further to 130° C.
  4. stirringthe reaction was stirred for another 45 minutes
  5. temperatureThe reaction was cooled to room temperature
  6. customThe layers were separated
  7. extractionthe aqueous was extracted with ethyl acetate (4×)
  8. washThe combined organics were washed with water and brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by flash column chromatography (20-70% ethyl acetate/heptanes)

Sources & evidence

ORD record
ord-9780fa3d9f9b454280602d78c79b1a4f
Source dataset
uspto-grants-2014_10
Patent number
US08859773B2

Reaction notes

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