Triethylamine → 2-(Allyloxy)-5-bromo-3-fluoroaniline

HRID 1373763Notes

Reaction equation

HRID 1373763 reaction equation
[CH2:1]([O:4][C:5]1[C:10]([N+:11]([O-])=O)=[CH:9][C:8]([Br:14])=[CH:7][C:6]=1[F:15])[CH:2]=[CH2:3].O.O.[Sn](Cl)(Cl)(Cl)Cl.C(N(CC)CC)C>C(O)C>[CH2:1]([O:4][C:5]1[C:6]([F:15])=[CH:7][C:8]([Br:14])=[CH:9][C:10]=1[NH2:11])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 210753692-(Allyloxy)-5-bromo-1-fluoro-3-nitrobenzeneHCID 85782573Tin tetrachloride dihydrate

Product 1

HCID 210753702-(Allyloxy)-5-bromo-3-fluoroanilineYield 55%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of Example 89A (1.3 g, 4.71 mmol), tin chloride dihydrate (5.3 g, 23.5 mmol) and triethylamine (13.1 mL, 94.2 mmol) in ethanol (50 mL) was heated at 70° C. for 6 hours, cooled. The insoluble material was filtered off and extensively washed with ethyl acetate. The combined filtrate was concentrated, and the residue was purified by flash chromatography eluting with 5% ethyl acetate in dichloromethane to provide the desired product (638 mg, 55%). MS (DCI/NH3) m/z 247.82 (M+H)+; 1H NMR (500 MHz, DMSO-D6) δ ppm 4.41 (d, J=5.93 Hz, 2 H) 5.20 (dd, J=10.45, 1.72 Hz, 1 H) 5.30 (dd, J=17.31, 1.72 Hz, 1 H) 5.43 (s, 2 H) 6.03 (m, 1 H) 6.56 (dd, J=10.29, 2.50 Hz, 1 H) 6.66 (dd, J=2.34, 1.72 Hz, 1 H).

Workup

  1. temperaturecooled
  2. filtrationThe insoluble material was filtered off
  3. washextensively washed with ethyl acetate
  4. concentrationThe combined filtrate was concentrated
  5. customthe residue was purified by flash chromatography
  6. washeluting with 5% ethyl acetate in dichloromethane

Sources & evidence

ORD record
ord-61392782b95547349001cfcc096bbd9e
Source dataset
uspto-grants-2007_01
Patent number
US07163939B2

Reaction notes

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