Ammonium Hydroxide → 6-(Difluoromethoxy)-1,3-benzothiazol-2-amine

HRID 1875879Notes

Reaction equation

HRID 1875879 reaction equation
[F:1][CH:2]([F:11])[O:3][C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1.[S-:12][C:13]#[N:14].[K+].BrBr.[OH-].[NH4+]>C(O)(=O)C>[F:1][CH:2]([F:11])[O:3][C:4]1[CH:10]=[CH:9][C:7]2[N:8]=[C:13]([NH2:14])[S:12][C:6]=2[CH:5]=1

Participants

6

Reactant 4

HCID 14923Ammonium HydroxideHCID 24408BromineHCID 516872Potassium thiocyanate2×HCID 7373634-(Difluoromethoxy)aniline

Product 1

HCID 195858986-(Difluoromethoxy)-1,3-benzothiazol-2-amineYield 87.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

To 4-(difluoromethoxy)aniline (9.55 g, 60 mmol) in acetic acid (90 mL) was added potassium thiocyanate (KSCN) (12.41 mL, 240 mmol). The mixture was stirred for 20 minutes (KSCN dissolved into solution). To this mixture bromine (3.08 mL, 60.0 mmol) in acetic acid (40 mL) was added dropwise over 20 minutes. The reaction was stirred at room temperature overnight. It was poured into a mixture of 800 ml ice water and 200 ml saturated ammonium hydroxide. The product was extracted with ethyl acetate (5×). The organics were combined, washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford 6-(difluoromethoxy)benzo[d]thiazol-2-amine (12.6 g, 52.4 mmol, 87% yield) as a yellow solid.

Workup

  1. stirringThe reaction was stirred at room temperature overnight
  2. extractionThe product was extracted with ethyl acetate (5×)
  3. washwashed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-cd592ada2b224168a6f628e095fefa53
Source dataset
uspto-grants-2012_11
Patent number
US08309577B2

Reaction notes

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