p-Diiodobenzene → HCID 66911955, compound

HRID 1752043Notes

Reaction equation

HRID 1752043 reaction equation
C([Li])CCC.I[C:7]1[CH:12]=[CH:11][C:10]([I:13])=[CH:9][CH:8]=1.[O:14]1[CH2:20][CH2:19][CH2:18][C:17](=[O:21])[CH2:16][CH2:15]1.[Cl-].[NH4+]>C1COCC1>[I:13][C:10]1[CH:11]=[CH:12][C:7]([C:17]2([OH:21])[CH2:18][CH2:19][CH2:20][O:14][CH2:15][CH2:16]2)=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 12208p-DiiodobenzeneHCID 25517Ammonium ChlorideHCID 642792oxepan-4-oneHCID 178418339Butyllithium

Product 1

HCID 66911955HCID 66911955, compoundYield 36.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Under an argon atmosphere, a solution of n-butyllithium (1.50 M, in hexane) (0.5 ml) was added dropwise to a solution of 1,4-diiodobenzene (250 mg) in anhydrous THF (3 ml) at −78° C., and the resulting mixture was stirred at −78° C. for 30 minutes. Oxepan-4-one (151 mg) was added to the reaction solution, and the resulting mixture was stirred at −78° C. for 1 hour. Saturated aqueous ammonium chloride solution was added thereto, and the resulting mixture was extracted with ethyl acetate. Organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was purified by column chromatography (silica gel, eluent: hexane/ethyl acetate=5/1) to obtain 4-(4-iodophenyl)oxepan-4-ol (89 mg). (2) Under an argon atmosphere, a solution of 4-(4-iodophenyl)oxepan-4-ol (86 mg) obtained in (1) in anhydrous DMF (1.0 mL) was added to a suspension of sodium hydride (60 wt %) (16 mg) in anhydrous DMF (1.0 ml) at 0° C., and the resulting mixture was stirred at 0° C. for 30 minutes. Methyl iodide (0.025 ml) was added dropwise to the reaction solution, and the resulting mixture was stirred at room temperature for 10 hours. Saturated brine was added thereto, and the resulting mixture was extracted 3 times with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was purified by column chromatography (silica gel, eluent: hexane/ethyl acetate=6/1) to obtain 4-(4-iodophenyl)-4-methoxyoxepane (63 mg).

Workup

  1. stirringthe resulting mixture was stirred at −78° C. for 1 hour
  2. extractionthe resulting mixture was extracted with ethyl acetate
  3. washOrganic layer was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. customAfter removing anhydrous sodium sulfate
  6. filtrationby filtration
  7. concentrationthe filtrate was concentrated
  8. customThe residue was purified by column chromatography (silica gel, eluent: hexane/ethyl acetate=5/1)

Sources & evidence

ORD record
ord-375f2e89774246eca5705613121d8506
Source dataset
uspto-grants-2015_10
Patent number
US09162988B2

Reaction notes

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