Iodine → 1-(p-Chlorophenyl)-1-[2-fluoro-3-(m-phenoxyphenyl)propenyl]cyclopropane

HRID 963825Notes

Reaction equation

HRID 963825 reaction equation
[O:1]([C:8]1[CH:9]=[C:10](Br)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Mg].II.C(O[CH2:22][C:23]([F:35])=[CH:24][C:25]1([C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=2)[CH2:27][CH2:26]1)(=O)C>O1CCCC1.O>[Cl:34][C:31]1[CH:30]=[CH:29][C:28]([C:25]2([CH:24]=[C:23]([F:35])[CH2:22][C:10]3[CH:11]=[CH:12][CH:13]=[C:8]([O:1][C:2]4[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=4)[CH:9]=3)[CH2:26][CH2:27]2)=[CH:33][CH:32]=1

Participants

7

Reactant 4

HCID 807IodineHCID 961653-Bromodiphenyl etherHCID 5462224MagnesiumHCID 543111381-(3-Acetoxy-2-fluoroprop-1-enyl)-1-(4-chlorophenyl)cyclopropane

Product 1

HCID 218358041-(p-Chlorophenyl)-1-[2-fluoro-3-(m-phenoxyphenyl)propenyl]cyclopropaneYield 22%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A Grignard reagent, prepared from 3-phenoxyphenyl bromide (0.33 g) in dry tetrahydrofuran (2 ml) and magnesium (30 mg) under nitrogen using iodine as an initiator at ca 40 C for 50 min, was cooled to room temperature then treated with cuprous bromide (ca 20 mg) for 10 min. After cooling to -78° C., a solution of 1-(3-acetoxy-2-fluoroprop-1-enyl)-1-(4-chlorophenyl)cyclopropane (Example 17) (0.32 g) in tetrahydrofuran was added slowly with stirring, then the mixture was allowed to warm to room temperature overnight. The mixture was treated with water (4 ml), then extracted with diethyl ether (3×20 ml). The combined organic extracts were washed with water (2×10 ml), dried, and evaporated under reduced pressure. The residue was purified by preparative thin layer chromatography (solvent: diethyl ether/hexane; 1:9) and then preparative high performance liquid chromatography (column: C18; solvent: methanol; flow rate: 8 ml/min) to afford 1-(4-chlorophenyl)-1-(2-fluoro-3-(3-phenoxyphenyl)prop-1-enyl)cyclopropane (98 mg, 22%).

Workup

  1. customfor 50 min
  2. temperatureAfter cooling to -78° C.
  3. temperatureto warm to room temperature overnight
  4. extractionextracted with diethyl ether (3×20 ml)
  5. washThe combined organic extracts were washed with water (2×10 ml)
  6. customdried
  7. customevaporated under reduced pressure
  8. customThe residue was purified by preparative thin layer chromatography (solvent: diethyl ether/hexane; 1:9)

Sources & evidence

ORD record
ord-14a21585a66540619d98c243914131d2
Source dataset
uspto-grants-1998_06
Patent number
US05763700

Reaction notes

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