Nitrogen → 2-Ethyl-4-fluoro-1-nitrobenzene

HRID 419350

Reaction equation

HRID 419350 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH2:12](B(O)O)[CH3:13].C([O-])([O-])=O.[K+].[K+].N#N>O1CCOCC1.O.CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:12]([C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10])[CH3:13]

Participants

9

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 521157Ethylboronic acidHCID 27569932-Bromo-4-fluoro-1-nitrobenzene

Product 1

HCID 212773652-Ethyl-4-fluoro-1-nitrobenzeneYield 24.2%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

2-Bromo-4-fluoro-1-nitrobenzene (21.8 g, 100 mmol), ethyl boronic acid (7.5 g, 100 mL), K2CO3 (40 g, 300 mL), dichloro[1,1′-bis(diphenylphosphino)-ferrocene]palladium (II) (6 g) in dioxane (250 mL) and H2O (80 mL) was flushed with N2 and heated at 100° C. overnight. The reaction was diluted with EtOAc and H2O and filtered through Celite®. The organic layer was separated, concentrated and purification by flash chromatography provided the title compound (4.1 g, 24.2 mmol, 24%). 1H NMR (400 MHz, CDCl3) δ ppm 1.30 (t, J=7.78, 3H), 2.92 (q, J=7.78, 2H), 7.01-7.11 (m, 2H), 7.98 (dd, J=8.53 Hz, J=5.53 Hz, 1H).

Workup

  1. filtrationfiltered through Celite®
  2. customThe organic layer was separated
  3. concentrationconcentrated
  4. custompurification by flash chromatography

Sources & evidence

ORD record
ord-1bcead23c36d43e8b2a566ac0018f095
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Linked notes

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