1-Fluoro-3-nitrobenzene → 2-Chloro-1-fluoro-3-nitrobenzene

HRID 2301653

Reaction equation

HRID 2301653 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:6][CH:7]=1.[Cl:11]N1C(=O)CCC1=O.C[Si]([N-][Si](C)(C)C)(C)C.[Na+]>C1COCC1>[Cl:11][C:3]1[C:2]([F:1])=[CH:7][CH:6]=[CH:5][C:4]=1[N+:8]([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 98231-Fluoro-3-nitrobenzeneHCID 31398ChlorosuccinimideHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 888832-Chloro-1-fluoro-3-nitrobenzeneYield 9.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a −78° C. solution of 3-fluoronitrobenzene (2 g, 14.2 mmol) in THF (30 mL) was added N-chlorosuccinimide (5.69 g, 42.6 mmol) in THF (20 mL), NaHMDS (1 M in THF, 28.4 mL, 28.4 mmol) was then added dropwise to maintain an internal temperature below −75° C. The resulting mixture was stirred for 30 min at −78° C. Then it was partitioned between 5% of HCl and ethyl acetate. The combined organic layer is dried over MgSO4 and filtered. The solvent was evaporated and chromatography of the resulting solid on silica gel (20% Ethyl acetate Hexane) gave the desired product(231 mg, 9.2%). EI-MS m/z 176.5 (M+).

Workup

  1. additionwas then added dropwise
  2. temperatureto maintain an internal temperature below −75° C
  3. customThen it was partitioned between 5% of HCl and ethyl acetate
  4. dry with materialThe combined organic layer is dried over MgSO4
  5. filtrationfiltered
  6. customThe solvent was evaporated

Sources & evidence

ORD record
ord-024e256dfd614b48956879219a3257c2
Source dataset
uspto-grants-2002_12
Patent number
US06500863B1

Linked notes

Loading…