Allylamine → Allyl-(3-fluoro-6-nitro-2-vinylphenyl)amine

HRID 243199Notes

Reaction equation

HRID 243199 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].[CH2:14]([NH2:17])[CH:15]=[CH2:16].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[CH2:14]([NH:17][C:4]1[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=[C:2]([F:1])[C:3]=1[CH:12]=[CH2:13])[CH:15]=[CH2:16]

Participants

5

Reactant 3

HCID 7853AllylamineHCID 11430Potassium CarbonateHCID 681573311,3-Difluoro-4-nitro-2-vinylbenzene

Product 1

HCID 68157050Allyl-(3-fluoro-6-nitro-2-vinylphenyl)amineYield 79.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1,3-difluoro-4-nitro-2-vinylbenzene (115 mg, 0.621 mmol) in DMF (3 mL) was added allylamine (0.0513 mL, 0.683 mmol) and potassium carbonate (0.173 g, 1.24 mmol). The reaction mixture was stirred at RT for 2 h, and then 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 1-5% EtOAc in cyclohexane) affording the title compound as a yellow oil (109.6 mg, 79%). 1H NMR (CDCl3, 300 MHz): 8.08 (1H, dd J=9.4, 5.8 Hz), 7.64 (1H, bs), 6.57 (1H, t, J=9.3 Hz), 6.51 (1H, dd, J=18.0, 11.6 Hz), 5.81 (1H, tdd, J=17.1, 10.2, 5.5 Hz), 5.72 (1H, ddd, J=18.0, 2.5, 1.6 Hz), 5.65 (1H, ddd, J=11.6, 1.5, 0.9 Hz), 5.26 (1H, dq, J=17.1, 1.5 Hz), 5.17 (1H, dq, J=10.2, 1.4 Hz), 3.98 (2H, ddt, J=6.3, 5.5, 1.6 Hz)

Workup

  1. custompartitioned between water and EtOAc
  2. extractionThe aqueous phase was extracted with EtOAc
  3. washthe combined organic layers were washed with water
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThe resulting residue was purified by column chromatography (Si—PCC, eluant 1-5% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-d50d73e8b533475f8eaac972bd098f52
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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