1,2-Dichloro-4-nitrobenzene → 7-(2-Chloro-4-nitrophenoxy)-2,2-dimethyl-2,3-dihydro-1-benzofuran

HRID 2295795Notes

Reaction equation

HRID 2295795 reaction equation
C(=O)([O-])[O-].[K+].[K+].[Cl:7][C:8]1[CH:9]=[C:10]([N+:15]([O-:17])=[O:16])[CH:11]=[CH:12][C:13]=1Cl.[CH3:18][C:19]1([CH3:29])[CH2:23][C:22]2[CH:24]=[CH:25][CH:26]=[C:27]([OH:28])[C:21]=2[O:20]1>CN(C=O)C>[Cl:7][C:8]1[CH:9]=[C:10]([N+:15]([O-:17])=[O:16])[CH:11]=[CH:12][C:13]=1[O:28][C:27]1[C:21]2[O:20][C:19]([CH3:29])([CH3:18])[CH2:23][C:22]=2[CH:24]=[CH:25][CH:26]=1

Participants

5

Reactant 3

HCID 74431,2-Dichloro-4-nitrobenzeneHCID 11430Potassium CarbonateHCID 152782,3-Dihydro-2,2-dimethyl-7-benzofuranol

Product 1

HCID 132459937-(2-Chloro-4-nitrophenoxy)-2,2-dimethyl-2,3-dihydro-1-benzofuranYield 95.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

To a mixture containing 32.63 g (0.236 mole) of anhydrous potassium carbonate and 30.41 g (0.158 mole) of 3,4-dichloro-1-nitrobenzene in 250 ml of dry DMF at room temperature and under an atmosphere of nitrogen was added 30.88 g (0.188 mole) of 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran. The reaction mixture was then placed in an oil bath and heated to 110° C. for 20 hours The reaction mixture was cooled to room temperature. The DMF was removed under vacuum. The residue was dissolved in 1.5 L of 1:1 ethylacetate:ether and 300 ml of water. The layers were separated. The organic layer was washed twice with 5% NaOH, twice with H2O and once with a saturated aqueous NaCl solution. After drying over anhydrous Na2SO4, removal of the solvents afforded 48.42 g of a light tan solid. This was recrystallized from hexane:ethyl acetate to afford 44.19 g of white crystals mp 132°-133° C. NMR (CDCl3): δ1.42 (s, 6H), 3.05 (s, 2H), 6.5-7.2 (m, 4H), 7.95 (doft, J=9, 2 Hz, 1H), 8.28 (d, J=2 Hz, 1H).

Workup

  1. customThe reaction mixture was then placed in an oil bath
  2. temperaturewas cooled to room temperature
  3. customThe DMF was removed under vacuum
  4. dissolutionThe residue was dissolved in 1.5 L of 1:1 ethylacetate
  5. customThe layers were separated
  6. washThe organic layer was washed twice with 5% NaOH, twice with H2O and once with a saturated aqueous NaCl solution
  7. dry with materialAfter drying over anhydrous Na2SO4, removal of the solvents

Sources & evidence

ORD record
ord-0fb593f5205b4b599d0200684afd0832
Source dataset
uspto-grants-1984_01
Patent number
US04426385

Reaction notes

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