Methyl iodide → 4-fluoro-3-methyl-6-nitro-1,3-benzoxazol-2(3H)-one

HRID 1991336Notes

Reaction equation

HRID 1991336 reaction equation
IC.[F:3][C:4]1[C:9]2[NH:10][C:11](=[O:13])[O:12][C:8]=2[CH:7]=[C:6]([N+:14]([O-:16])=[O:15])[CH:5]=1.N12CCCN=C1CCCC[CH2:18]2>CN(C=O)C.C(OCC)(=O)C>[F:3][C:4]1[C:9]2[N:10]([CH3:18])[C:11](=[O:13])[O:12][C:8]=2[CH:7]=[C:6]([N+:14]([O-:16])=[O:15])[CH:5]=1

Participants

6

Reactant 3

HCID 6328Methyl iodideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 684892924-fluoro-6-nitro-1,3-benzoxazol-2(3H)-one

Product 1

HCID 684871524-fluoro-3-methyl-6-nitro-1,3-benzoxazol-2(3H)-oneYield 83.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

Iodomethane (0.393 ml, 6.31 mmol) is added in portions to crude 4-fluoro-6-nitro-1,3-benzoxazol-2(3H)-one (Step 5, 1.00 g, 5.05 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.94 ml, 6.31 mmol) in DMF (10 ml). The reaction is stirred at 65° C. overnight, diluted with ethyl acetate, washed with 2N HCl and saline, dried (MgSO4), and evaporated to give crude product containing trace amounts of undesired 5-nitro isomer. Purification by flash column chromatography (20% ethyl acetate/hexane) gives pure product as a white solid (0.89 g, 83%); mp 118-9° C.

Workup

  1. washwashed with 2N HCl and saline
  2. dry with materialdried (MgSO4)
  3. customevaporated
  4. customto give crude product
  5. additioncontaining trace amounts of undesired 5-nitro isomer
  6. customPurification by flash column chromatography (20% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-8282183087ff4b039ed88e9d7cefc12b
Source dataset
uspto-grants-2010_01
Patent number
US07645781B2

Reaction notes

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