Potassium Carbonate → (3-Fluoro-6-nitro-2-vinylphenyl)-(1-methylallyl)amine

HRID 243212Notes

Reaction equation

HRID 243212 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4](F)[C:3]=1[CH:12]=[CH2:13].[CH3:14][CH:15]([NH2:18])[CH:16]=[CH2:17].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.C(O)C>[F:1][C:2]1[C:3]([CH:12]=[CH2:13])=[C:4]([NH:18][CH:15]([CH3:14])[CH:16]=[CH2:17])[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 15584178But-3-en-2-amine2×HCID 681573311,3-Difluoro-4-nitro-2-vinylbenzene

Product 1

HCID 68157256(3-Fluoro-6-nitro-2-vinylphenyl)-(1-methylallyl)amineYield 70%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1,3-difluoro-4-nitro-2-vinylbenzene (150 mg, 0.81 mmol) in DMF (3 mL) was added a mixture of 1-methylallylamine in ethanol (0.4 mL). Potassium carbonate (0.224 g, 1.62 mmol) was added and the mixture stirred at RT for 1 h. A further portion of 1-methylallylamine in ethanol (0.3 mL) was added and stirring was continued for 1 h, and then the reaction mixture was partitioned between water and EtOAc. The aqueous phase was extracted with EtOAc and the combined organic layers were washed with water, followed by brine, then dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PCC, eluant 2-6% EtOAc in cyclohexane) affording the title compound as a yellow oil (134 mg, 70%). 1H NMR (CDCl3, 300 MHz): 8.06 (1H, dd J=9.4, 5.7 Hz), 7.23 (1H, bs), 6.62 (1H, t, J=9.3 Hz), 6.48 (1H, dd, J=18.0, 11.6 Hz), 5.81-5.62 (2H, m), 5.64 (1H, dt, J=11.6, 1.3 Hz), 5.12-5.00 (2H, m), 4.38-4.25 (1H, m), 1.27 (3H, d, J=6.6 Hz)

Workup

  1. stirringstirring
  2. waitwas continued for 1 h
  3. customthe reaction mixture was partitioned between water and EtOAc
  4. extractionThe aqueous phase was extracted with EtOAc
  5. washthe combined organic layers were washed with water
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customThe resulting residue was purified by column chromatography (Si—PCC, eluant 2-6% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-f955077789a94d00889469c01a245820
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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