Hydrazine → HCID 59375012, compound

HRID 1811032Notes

Reaction equation

HRID 1811032 reaction equation
[Br:1][C:2]1[C:3]([CH3:18])=[C:4]([NH:8][C:9](=S)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2F)[CH:5]=[CH:6][CH:7]=1.[NH2:19][NH2:20]>CS(C)=O.C([O-])(O)=O.[Na+]>[Br:1][C:2]1[C:3]([CH3:18])=[C:4]([NH:8][C:9]2[C:10]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[NH:20][N:19]=2)[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 9321HydrazineHCID 86642943HCID 86642943, compound

Product 1

HCID 59375012HCID 59375012, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
150 °C

Procedure

Step 3 A yellow solution of N-(3-bromo-2-methylphenyl)-2-fluorobenzothioamide (500 mg, 1.542 mmol) in DMSO (5 mL) was treated with anhydrous hydrazine (0.484 mL, 15.42 mmol) and heated at 150° C. After 2 h 20 min the solution was cooled to rt, diluted with NaHCO3 (aq) and extracted twice with EtOAc. The combined organic phases were washed twice with water and once with brine, dried and concentrated. The residue was purified by column chromatography (eluting with a gradient from 85:15 to 50:50 hexane-EtOAc) to provide N-(3-bromo-2-methylphenyl)-1H-indazol-3-amine as a tan waxy solid (162 mg, 35%). 1H NMR (400 MHz, chloroform-d) δ 9.38 (1 H, br. s.), 7.49 (1 H, d, J=8.1 Hz), 7.45 (1 H, d, J=7.9 Hz), 7.40 (2 H, d, J=3.5 Hz), 7.19 (1 H, dd, J=7.9, 0.9 Hz), 7.10 (1 H, dt, J=8.1, 4.0 Hz), 6.98 (1 H, t, J=8.1 Hz), 6.10 (1 H, s), 2.49 (3 H, s). Mass spectrum m/z 302, 304 (M+H)+.

Workup

  1. temperatureAfter 2 h 20 min the solution was cooled to rt
  2. extractionextracted twice with EtOAc
  3. washThe combined organic phases were washed twice with water and once with brine
  4. customdried
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (
  7. washeluting with a gradient from 85:15 to 50:50 hexane-EtOAc)

Sources & evidence

ORD record
ord-6948a35ce41a4ec588527f1b677a55b6
Source dataset
uspto-grants-2013_01
Patent number
US08362065B2

Reaction notes

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