Tert-Butyl nitrite → 1022151-31-0

HRID 1890914Notes

Reaction equation

HRID 1890914 reaction equation
[Br:1][C:2]1[C:11]([F:12])=[CH:10][C:5]2[N:6]=[C:7](N)[S:8][C:4]=2[CH:3]=1.C(ON=O)(C)(C)C>CN(C=O)C>[Br:1][C:2]1[C:11]([F:12])=[CH:10][C:5]2[N:6]=[CH:7][S:8][C:4]=2[CH:3]=1

Participants

4

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 754809671022151-32-1

Product 1

HCID 579109931022151-31-0Yield 52%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 6-bromo-5-fluoro-benzothiazol-2-ylamine (2.73 g, 11.05 mmol) in DMF (60 mL) was added tert-butylnitrite (1.58 mL, 13.26 mmol) dropwise. The reaction mixture was stirred at 50° C. for 3 h, then it was concentrated in vacuo. The residue was stirred in 1 N aqueous KOH for 10 min, then ethyl acetate was added and the mixture was stirred overnight. The insolubles were filtered, washed with water then ethyl acetate. The resulting filtrate was separated, and the organic layer was washed with brine and directly adsorbed on silica gel. Purification by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate/hexane afforded 1.33 g of 6-bromo-5-fluoro-benzothiazole as a light yellow solid (52% yield): 1H NMR (DMSO-d6) δ 8.13 (d, 1H), 8.63 (d, 1H), 9.50 (s, 1H); MS (m/z) 232, 234 [M+H+]+.

Workup

  1. concentrationit was concentrated in vacuo
  2. stirringThe residue was stirred in 1 N aqueous KOH for 10 min
  3. additionethyl acetate was added
  4. stirringthe mixture was stirred overnight
  5. filtrationThe insolubles were filtered
  6. washwashed with water
  7. customThe resulting filtrate was separated
  8. washthe organic layer was washed with brine
  9. customPurification by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate/hexane

Sources & evidence

ORD record
ord-1fe29267e2644368ba49d1b60687d89b
Source dataset
uspto-grants-2013_08
Patent number
US08507489B2

Reaction notes

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