(3-Fluoro-6-nitro-2-vinylphenyl)-(1-methylallyl)amine → 5-Fluoro-2-methyl-8-nitro-1,2-dihydroquinoline

HRID 243213Notes

Reaction equation

HRID 243213 reaction equation
[F:1][C:2]1[C:3]([CH:16]=[CH2:17])=[C:4]([NH:11][CH:12]([CH3:15])C=C)[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1>C(Cl)Cl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]2[C:3]=1[CH:16]=[CH:17][CH:12]([CH3:15])[NH:11]2

Participants

4

Reactant 1

HCID 68157256(3-Fluoro-6-nitro-2-vinylphenyl)-(1-methylallyl)amine

Product 1

HCID 681574055-Fluoro-2-methyl-8-nitro-1,2-dihydroquinolineYield 65.1%

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of (3-fluoro-6-nitro-2-vinylphenyl)-(1-methylallyl)amine (134 mg, 0.567 mmol) in DCM (10 mL) was added Grubbs catalyst (2nd generation, benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium) (9.6 mg, 0.011 mmol). The reaction mixture was stirred at RT for 64 h, and then purified by column chromatography (Si—PCC, eluant 1-4% EtOAc in cyclohexane) affording recovered starting material (56 mg) and the title compound (62.8 mg). The recovered starting material was dissolved in DCM (10 mL) and Grubbs catalyst (2nd generation, benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium) (12 mg) was added. The reaction mixture was stirred at 45° C. for 16 h, and then purified by column chromatography (Si—PCC, DCM). The combined products were further purified by column chromatography (Si—PCC, eluant 1.5-4% EtOAc in cyclohexane) affording the title compound as a red solid (76.8 mg, 65%). 1H NMR (CDCl3, 300 MHz): 8.26 (1H, bs), 7.92 (1H, dd, J=9.6, 6.0 Hz), 6.53 (1H, dd, J=10.2, 1.7 Hz), 6.24 (1H, dd, J=9.7, 8.4 Hz), 5.70-5.65 (1H, m), 4.72-4.63 (1H, m), 1.43 (3H, J=6.6 Hz)

Workup

  1. custompurified by column chromatography (Si—PCC, eluant 1-4% EtOAc in cyclohexane)
  2. customaffording
  3. customrecovered
  4. dissolutionwas dissolved in DCM (10 mL)
  5. additionGrubbs catalyst (2nd generation, benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium) (12 mg) was added
  6. stirringThe reaction mixture was stirred at 45° C. for 16 h
  7. custompurified by column chromatography (Si—PCC, DCM)
  8. customThe combined products were further purified by column chromatography (Si—PCC, eluant 1.5-4% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-f783bd37134f4834adb64e894d4d5a27
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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