1-Naphthoic acid → 4-Chloro-2-methoxy-1-phenoxybenzene

HRID 2246758Notes

Reaction equation

HRID 2246758 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([OH:15])=[C:11]([O:16][CH3:17])[CH:10]=1.C([O-])([O-])=O.[Cs+].[Cs+].C(OCC)(=O)C.C1(C(O)=O)C2C(=CC=CC=2)C=CC=1>C1C=CC=CC=1.FC(F)(F)S([O-])(=O)=O.[Cu+].C1(C)C=CC=CC=1>[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:11]([O:16][CH3:17])[CH:10]=1

Participants

8

Reactant 5

HCID 68471-Naphthoic acidHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 11575IodobenzeneHCID 280504-Chloroguaiacol

Product 1

HCID 586041314-Chloro-2-methoxy-1-phenoxybenzene

Reagents, catalysts & solvents 2

HCID 11392160copper(I) trifluoromethanesulfonate benzeneCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

Iodobenzene (7.35 mmol), 4-chloro-2-methoxyphenol (14.7 mmol), Cs2CO3 (32.3 mmol), copper(I) trifluoromethanesulfonate benzene complex (0.735 mmol, 5.0 mol % Cu), ethyl acetate (0.125 mmol, 5.0 mol %), 1-naphthoic acid (32.3 mmol), molecular sieves 4A (1.8 g) and toluene (15 mL) were added to an oven-dried 50 mL two-necked round-bottomed flask. The flask was sealed with a rubber septum, purged with nitrogen, and the temperature raised to 110° C. overnight and monitored by thin layer chromatography. The solution was cooled to room temperature, followed by the addition of 50 mL dichloromethane. The solution was filtered and then washed with a 5% sodium hydroxide aqueous solution. The aqueous layer was then extracted with dichloromethane and the combined organic layers washed with brine (NaCl). The organic phase was dried over anhydrous Mg2SO4 and concentrated under vacuum to give the crude product. Purification by flash chromatography on silica gel afforded the analytically pure compound (3): 1H NMR (300 MHz) (CDCl3): δ 7.35-6.94 (m, 8H), 3.86 (s, 3H).

Workup

  1. customThe flask was sealed with a rubber septum
  2. custompurged with nitrogen
  3. temperatureThe solution was cooled to room temperature
  4. additionfollowed by the addition of 50 mL dichloromethane
  5. filtrationThe solution was filtered
  6. washwashed with a 5% sodium hydroxide aqueous solution
  7. extractionThe aqueous layer was then extracted with dichloromethane
  8. washthe combined organic layers washed with brine (NaCl)
  9. dry with materialThe organic phase was dried over anhydrous Mg2SO4
  10. concentrationconcentrated under vacuum
  11. customto give the crude product
  12. customPurification by flash chromatography on silica gel

Sources & evidence

ORD record
ord-ff274e68f3d34bc0bb75e3ab6e3e7c34
Source dataset
uspto-grants-2010_03
Patent number
US07687547B2

Reaction notes

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