3-Fluoroaniline → 3-Fluoro-4-iodoaniline

HRID 1429205Notes

Reaction equation

HRID 1429205 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][CH:8]=1)[NH2:5].C(=O)(O)[O-].[Na+].CO.ClCCl.[I:19](Cl)(=O)=O.I(Cl)(=O)=O.C([N+](C)(C)C)C1C=CC=CC=1>ClCCl>[F:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[I:19])[NH2:5]

Participants

6

Reactant 4

HCID 97423-FluoroanilineHCID 516892Sodium BicarbonateHCID 21226129Dichloromethane methanolHCID 56924451Trimethylbenzylammonium Dichloroiodate

Product 1

HCID 154755463-Fluoro-4-iodoanilineYield 89.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of 3-fluoroaniline (1.0 mL, 1.16 g, 10.39 mmol) and solid sodium bicarbonate (1.75 g, 20.79 mmol) in 1:1 methanol-dichloromethane (20 mL) at 0° C. was added a solution of benzyl trimethylammonium dichloroiodate (3.62 g, 10.39 mmol) in dichloromethane (15 mL) over 30 minutes. The mixture was then allowed to warm to room temperature for 1 hour. The mixture was quenched by addition of water and the organic layer was extracted with water (2×). Drying (Na2SO4) and concentration in vacuo afforded an oil, which was chromatographed over a 100 g silica gel cartridge, eluting with 10-100% ethyl acetate in hexanes. These procedures afforded the title compound (2.20 g, 89%) as a pink solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.41 (dd, J=8.3, 7.3 Hz, 1 H), 6.42 (dd, J=9.9, 2.5 Hz, 1 H), 6.27 (dd, J=8.5, 2.5 Hz; 1 H), 3.81 (s, 2 H); MS+ESI m/z (rel abundance) 238 (100, M+H).

Workup

  1. customThe mixture was quenched by addition of water
  2. extractionthe organic layer was extracted with water (2×)
  3. customDrying
  4. concentration(Na2SO4) and concentration in vacuo
  5. customafforded an oil, which
  6. customwas chromatographed over a 100 g silica gel cartridge
  7. washeluting with 10-100% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-91a0fa271e7c4020a51ad3073e2b7adb
Source dataset
uspto-grants-2015_01
Patent number
US08937150B2

Reaction notes

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