1,3-Benzenediol, propyl- → HCID 10518590, compound

HRID 1977919Notes

Reaction equation

HRID 1977919 reaction equation
[CH2:1]([C:4]1[C:10]([OH:11])=[CH:9][CH:8]=[CH:7][C:5]=1[OH:6])[CH2:2][CH3:3].CC(C)([O-])C.[K+].Br[C:19]1[CH:28]=[C:27]([F:29])[CH:26]=[CH:25][C:20]=1[C:21]([O:23][CH3:24])=[O:22]>N1C=CC=CC=1.[Cu]I>[CH3:24][O:23][C:21](=[O:22])[C:20]1[CH:19]=[CH:28][C:27]([F:29])=[CH:26][C:25]=1[O:11][C:10]1[CH:9]=[CH:8][CH:7]=[C:5]([OH:6])[C:4]=1[CH2:1][CH2:2][CH3:3]

Participants

6

Reactant 3

HCID 2620601,3-Benzenediol, propyl-HCID 7210837Methyl 2-bromo-4-fluorobenzoateHCID 23665647Potassium tert-butoxide

Product 1

HCID 10518590HCID 10518590, compoundYield 15%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1049PyridineSolvent2×

Procedure

To a solution of 2-propylresorcinol (10.0 g, 65.7 mmol) in pyridine (120 mL) was added potassium tert-butoxide (7.00 g, 62.5 mmol) at room temperature with stirring. To this was added a mixture of methyl 2-bromo-4-fluorobenzoate (7.60 g, 32.6 mmol) and copper(I) iodide (12.5 g, 65.7 mmol) in pyridine (120 mL). The resulting mixture was gently refluxed for 4 hours. The reaction was cooled to room temperature and stirred for 18 hours. The mixture was concentrated in vacuo and the resulting material dissolved in ethyl ether. The solution was washed once with 5N aqueous hydrochloric acid. The aqueous layer was extracted once with fresh ethyl ether and the combined organic layers were washed twice with 5N aqueous ammonium hydroxide. The organic layer was washed once with a saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated in vacuo. Silica gel chromatography of the resulting residue provided 1.45 g (15%) of the desired intermediate product as a light tan solid: mp 92-94° C.; NMR (CDCl3) 7.95 (m, 1H), 7.04 (t, J=9.5 Hz, 1H), 6.79 (t, J=9 Hz, 1H), 6.65 (d, J=9.5 Hz, 1H), 6.50 (m, 2H), 5.25 (bs, 1H, —OH), 3.88 (s, 3H), 2.60 (t, J=8.7 Hz, 2H), 1.55 (hextet, J=7.8 Hz, 2H), 0.92 (t, J=7.8 Hz, 3H); MS-FD m/e 305 (p+1, 40), 304 (p, 100); IR.

Workup

  1. additionTo this was added
  2. temperatureThe resulting mixture was gently refluxed for 4 hours
  3. stirringstirred for 18 hours
  4. concentrationThe mixture was concentrated in vacuo
  5. dissolutionthe resulting material dissolved in ethyl ether
  6. washThe solution was washed once with 5N aqueous hydrochloric acid
  7. extractionThe aqueous layer was extracted once with fresh ethyl ether
  8. washthe combined organic layers were washed twice with 5N aqueous ammonium hydroxide
  9. washThe organic layer was washed once with a saturated sodium chloride solution
  10. dry with materialdried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-196092ed36384b2ca9bafd6bb28b2840
Source dataset
uspto-grants-2001_05
Patent number
US06235785B1

Reaction notes

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