HCID 68157662, compound → HCID 68157807, compound

HRID 243206

Reaction equation

HRID 243206 reaction equation
[CH2:1]([NH:5][C:6]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[C:8]([F:15])[C:7]=1[CH:16]=[CH2:17])[CH2:2]C=C>C(Cl)Cl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl.Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1>[F:15][C:8]1[C:7]2[CH:16]=[CH:17][CH2:2][CH2:1][NH:5][C:6]=2[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=1

Participants

5

Reactant 1

HCID 68157662HCID 68157662, compound

Product 1

HCID 68157807HCID 68157807, compoundYield 78.1%

Reagents, catalysts & solvents 3

HCID 178425456HCID 178425456, compoundCatalystHCID 178479819HCID 178479819, compoundCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

To a solution of but-3-enyl-(3-fluoro-6-nitro-2-vinylphenyl)amine (327.6 mg, 1.386 mmol) in DCM (30 mL) was added Grubbs catalyst (2nd generation, benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium) (47 mg, 0.055 mmol). The reaction mixture was stirred at RT for 16 h, and then a further portion of the Grubbs catalyst (47 mg, 0.055 mmol) was added and stirring continued for a further 64 h. The reaction mixture was concentrated in vacuo and then purified by column chromatography (Si—PCC, eluant 2-6% EtOAc in cyclohexane). The recovered starting material (145 mg) was dissolved in DCM (20 mL) and Grubbs 2nd generation catalyst (30 mg, 0.035 mmol) was added. The reaction mixture was heated under reflux for 6 h, then left at RT for 16 h. The reaction mixture was concentrated in vacuo, combined with the product from the initial purification and purified by column chromatography (Si—PCC, eluant 2-8% EtOAc in cyclohexane) affording the title compound as a red solid (225.4 mg, 78%). 1H NMR (CDCl3, 300 MHz): 8.90 (1H, bs), 8.09 (1H, dd, J=9.4, 6.0 Hz), 6.67 (1H, dt, J=12.3, 1.8 Hz), 6.47 (1H, t, J=9.6 Hz), 6.16 (1H, dt, J=12.3, 4.7 Hz), 3.52 (2H, q, J=4.9 Hz), 2.65 (2H, dq, J=4.8, 1.8 Hz)

Workup

  1. stirringstirring
  2. waitcontinued for a further 64 h
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. custompurified by column chromatography (Si—PCC, eluant 2-6% EtOAc in cyclohexane)
  5. dissolutionwas dissolved in DCM (20 mL)
  6. temperatureThe reaction mixture was heated
  7. temperatureunder reflux for 6 h
  8. waitleft at RT for 16 h
  9. concentrationThe reaction mixture was concentrated in vacuo
  10. custompurification
  11. custompurified by column chromatography (Si—PCC, eluant 2-8% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-30004aa67be14d7f94c6c941b14c4533
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Linked notes

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