Sodium Dithionite → HCID 86669366, compound

HRID 574090Notes

Reaction equation

HRID 574090 reaction equation
[CH2:1]([O:4][C:5]1[C:6]([N+:22]([O-])=O)=[C:7]([NH:13][C:14]2[CH:19]=[CH:18][C:17]([Br:20])=[CH:16][C:15]=2[F:21])[C:8]([F:12])=[C:9]([F:11])[CH:10]=1)[CH:2]=[CH2:3].[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(O)C.O>[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([F:11])[C:8]([F:12])=[C:7]([NH:13][C:14]2[CH:19]=[CH:18][C:17]([Br:20])=[CH:16][C:15]=2[F:21])[C:6]=1[NH2:22])[CH:2]=[CH2:3]

Participants

5

Reactant 2

HCID 24489Sodium DithioniteHCID 86669359HCID 86669359, compound2×

Product 1

HCID 86669366HCID 86669366, compoundYield 99.3%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

A suspension of (3-allyloxy-5,6-difluoro-2-nitro-phenyl)-(4-bromo-2-fluoro-phenyl)-amine (Intermediate 8, 0.7 g, 1.7 mmol) in ethanol (12 mL) was stirred at 70° C. to obtain a clear solution. To this hot solution, was added a freshly prepared solution of Na2S2O4 (0.9 g, 5.2 mmol) in water (1.9 mL) and stirred the reaction mixture at 90° C. for 1 h. The progress of reaction was monitored by TLC. After completion, the solvent was removed under reduced pressure. The residue was dissolved in ethyl acetate, washed with water, dried over anhydrous Na2SO4 and concentrated to yield 6-allyloxy-N2-(4-bromo-2-fluoro-phenyl)-3,4-difluoro-benzene-1,2-diamine as a yellow solid (630 mg). 1H-NMR (400 MHz, CDCl3): δ 4.55 (2H, d, J=5.6), 5.32-5.36 (2H, m), 5.42 (1H, d), 6.02-6.08 (1H, m), 6.35 (1H, t, J=8.8), 6.60-6.65 (1H, m), 7.06 (1H, d, J=8.4), 7.23 (1H, dd, J=2.0, 10.4).

Workup

  1. customto obtain a clear solution
  2. stirringstirred the reaction mixture at 90° C. for 1 h
  3. customThe progress of reaction
  4. customAfter completion, the solvent was removed under reduced pressure
  5. dissolutionThe residue was dissolved in ethyl acetate
  6. washwashed with water
  7. dry with materialdried over anhydrous Na2SO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-f8a9e9c545a546b187328f1636ab5e4f
Source dataset
uspto-grants-2015_05
Patent number
US09034861B2

Reaction notes

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