Ethanol → 4-Fluoro-2-(1-methylethoxy)benzenamine

HRID 633364Notes

Reaction equation

HRID 633364 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-])=O)=[C:4]([O:11][CH:12]([CH3:14])[CH3:13])[CH:3]=1.CCO.CC1C=C2N=C3C(=NC(NC3=O)=O)N(C[C@H](O)[C@H](O)[C@H](O)CO)C2=CC=1C>O.[Pd]>[F:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([O:11][CH:12]([CH3:14])[CH3:13])[CH:3]=1

Participants

6

Reactant 3

HCID 702EthanolHCID 493570RiboflavinHCID 106318324-Fluoro-2-isopropoxy-1-nitrobenzene

Product 1

HCID 37563854-Fluoro-2-(1-methylethoxy)benzenamineYield 98%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Procedure

A round-bottom flask was charged with 4-fluoro-2-isopropoxy-1-nitrobenzene (49.3 g, 248 mmol), EtOH (600 mL), and 10% Pd/C (50% in water, Degussa type E101; 10 g, 20 wt % by weight of the starting nitro compound). The flask was sealed with a rubber septum, degassed, and back-filled with H2 (×3) from a balloon filled with H2. The reaction was stirred for 4 d using a H2 filled balloon. The reaction mixture was filtered through a pad of celite, and the pad of celite was rinsed with MeOH. The filtrate was evaporated to dryness to provide 4-fluoro-2-isopropoxybenzenamine (41.0 g, 98%) as a brown liquid that was used without further purification. 1H NMR (300 MHz; d6-DMSO) δ 6.67-6.72 (dd, 1H, J=2.7 Hz, 11 Hz), 6.55-6.60 (dd, 1H, J=6.0 Hz, 8.7 Hz), 6.43-6.49 (td, 1H, J=2.7 Hz, 8.4 Hz), 4.47-4.55 (m, 3H), 1.23-1.25 (d, 6H, J=6.0 Hz); 19F NMR (282 MHz; d6-DMSO) δ −127.4 (sextet); m/z=170 (M+H)+.

Workup

  1. customThe flask was sealed with a rubber septum
  2. customdegassed
  3. additionback-filled with H2 (×3) from a balloon
  4. additionfilled with H2
  5. filtrationThe reaction mixture was filtered through a pad of celite
  6. washthe pad of celite was rinsed with MeOH
  7. customThe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-265d57f0f1a947609e780bb983bf2881
Source dataset
uspto-grants-2016_04
Patent number
US09321763B2

Reaction notes

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