Sodium;3-oxidodioxaborirane;tetrahydrate → 3-Chloro-5-fluoro-4-nitrobenzonitrile

HRID 715509Notes

Reaction equation

HRID 715509 reaction equation
B1([O-])OO1.[OH2:5].[OH2:6].O.O.[Na+].[NH2:10][C:11]1[C:18]([F:19])=[CH:17][C:14]([C:15]#[N:16])=[CH:13][C:12]=1[Cl:20]>C(O)(=O)C>[Cl:20][C:12]1[CH:13]=[C:14]([CH:17]=[C:18]([F:19])[C:11]=1[N+:10]([O-:6])=[O:5])[C:15]#[N:16]

Participants

4

Reactant 2

HCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate3×HCID 680399954-Amino-3-chloro-5-fluorobenzonitrile

Product 1

HCID 711161323-Chloro-5-fluoro-4-nitrobenzonitrile

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
60 °C

Procedure

Sodium perborate tetrahydrate (131 g, 851 mmol) in acetic acid (200 mL) was heated to 60° C. A solution of 4-amino-3-chloro-5-fluorobenzonitrile (29.02 g, 170 mmol) in acetic acid (500 mL) was added dropwise and the reaction was stirred at 60° C. for 16 h. The LCMS the indicated the reaction showed ˜50% conversion. Additional sodium perborate tetrahydrate (14.4 g) was added and the reaction stirred at 70° C. for 2 h. Then additional sodium perborate tetrahydrate (70 g) was added and the reaction was stirred at 80° C. for 5 h, followed by RT for 2 days. The reaction was then poured into ice water and extracted with EtOAc (3×). The combined organic extracts were washed with H2O (2×), brine, dried over MgSO4 and concentrated. When most of the acetic acid was evaporated, water was added to the residue. The orange precipitate was collected by filtration, washed with H2O and air dried to give the crude product as an orange solid. NMR showed the product contaminated with ˜10% of starting material. This product was used without any further purification.

Workup

  1. stirringthe reaction stirred at 70° C. for 2 h
  2. stirringthe reaction was stirred at 80° C. for 5 h
  3. waitfollowed by RT for 2 days
  4. extractionextracted with EtOAc (3×)
  5. washThe combined organic extracts were washed with H2O (2×), brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customWhen most of the acetic acid was evaporated
  9. additionwater was added to the residue
  10. filtrationThe orange precipitate was collected by filtration
  11. washwashed with H2O and air
  12. customdried

Sources & evidence

ORD record
ord-87a1d6c369984a27a87fd261f167c249
Source dataset
uspto-grants-2015_11
Patent number
US09187464B2

Reaction notes

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