3,4-Dimethylphenol → HCID 15324948, compound

HRID 1937804Notes

Reaction equation

HRID 1937804 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH3:13][C:14]1[CH:15]=[C:16]([OH:21])[CH:17]=[CH:18][C:19]=1[CH3:20].C([O-])([O-])=O.[Cs+].[Cs+]>C1C=CC=CC=1.C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH3:13][C:14]1[CH:15]=[C:16]([CH:17]=[CH:18][C:19]=1[CH3:20])[O:21][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 72493,4-DimethylphenolHCID 10796Cesium carbonateHCID 22043Ethyl 4-bromobenzoate

Product 1

HCID 15324948HCID 15324948, compoundYield 63%

Reagents, catalysts & solvents 3

HCID 241BenzeneCatalystHCID 8857Ethyl AcetateCatalystHCID 1140TolueneSolvent

Procedure

Ethyl 4-bromobenzoate (2.5 mmol), 3,4-dimethylphenol (3.5 or 5.0 mmol), molecular sieves (625 mg), Cs2CO3 (3.5 or 5.0 mmol), (CuOTf)2.PhH (0.0625 mmol, 5.0 mol % Cu), ethyl acetate (0.125 mmol, 5.0 mol %), and toluene (2.0 mL) were added to an oven-dried test tube which was then sealed with a septum, purged with argon, and heated to 110 C under argon until the aryl halide was consumed as determined by GC analysis. The reaction mixture was then allowed to cool to room temperature, diluted with Et2O and washed sequentially with 5% aqueous NaOH, water and brine. The organic layer was dried over Mg2SO4 and concentrated under vacuum to give the crude product. Purification by flash column chromatography (1% Et2O/pentane) gave the analytically pure product as a clear oil (425 mg, 63% yield). 1H NMR (300 MHz, CDCl3) δ 7.98 (d, J=8.6 Hz, 2H), 7.12 (d, J 8.0 Hz, 1H), 6.95 (d, J=8.6 Hz, 2H), 6.85 (d, J=2.4 Hz, 1H), 6.79 (dd, J=8.0 Hz, 2.3 Hz, 1H), 4.35 (q, J=7.0 Hz, 2H), 2.25 (s, 6H), 1.37 (t, J=7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 166.1, 162.2, 153.3, 138.5, 132.8, 131.5, 130.8, 124.4, 121.3, 117.4, 116.8, 60.7, 19.9, 19.1, 14.3; IR (neat): 2978, 2931, 1713, 1595, 1495, 1367, 1261, 1226, 1161, 1102 cm−1. Anal. Calcd for C17H18O3: C, 75.53; H, 6.71. Found: C, 75.77; H, 6.67.

Workup

  1. customwas then sealed with a septum
  2. custompurged with argon
  3. temperatureheated to 110 C under argon until the aryl halide
  4. customwas consumed
  5. additiondiluted with Et2O
  6. washwashed sequentially with 5% aqueous NaOH, water and brine
  7. dry with materialThe organic layer was dried over Mg2SO4
  8. concentrationconcentrated under vacuum
  9. customto give the crude product
  10. customPurification by flash column chromatography (1% Et2O/pentane)

Sources & evidence

ORD record
ord-d192a3a85e114109a46fe1136996be6f
Source dataset
uspto-grants-2002_05
Patent number
US06395939B1

Reaction notes

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