4-Methylmorpholine → 3-(2-Methoxyphenylsulfonyloxy)-5-methylphenol

HRID 442913Notes

Reaction equation

HRID 442913 reaction equation
CN1CCOCC1.Cl[C:9]1[CH:10]=[CH:11][C:12]([O:27][CH3:28])=[C:13]([S:15]([O:18][C:19]2[CH:20]=[C:21]([OH:26])[CH:22]=[C:23]([CH3:25])[CH:24]=2)(=[O:17])=[O:16])[CH:14]=1>[Pd].CO>[CH3:28][O:27][C:12]1[CH:11]=[CH:10][CH:9]=[CH:14][C:13]=1[S:15]([O:18][C:19]1[CH:20]=[C:21]([OH:26])[CH:22]=[C:23]([CH3:25])[CH:24]=1)(=[O:16])=[O:17]

Participants

5

Reactant 2

HCID 79724-MethylmorpholineHCID 227225683-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenol

Product 1

HCID 227224733-(2-Methoxyphenylsulfonyloxy)-5-methylphenolYield 63%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

4-Methylmorpholine (3.2 mL, 29.1 mmol) was added to a mixture of 3-(5-chloro-2- methoxyphenylsulfonyloxy)-5-methylphenol (8.82 g, 26.8 mmol, as prepared in the preceding step) and 10% palladium on carbon (2.23 g) in deoxygenated methanol (15 mL). The mixture was hydrogenated (atmospheric pressure) at ambient temperature for 3 h then filtered through Celite with methanol. Solvent was removed in vacuo and the crude product was purified by flash column chromatography (dichloromethane to 5% ethyl acetate in dichloromethane) to give the title compound (4.97 g, 63%) as a colorless syrup. 1H-NMR (300 MHz, DMSO-d,) δ 9.71 (s, 1 H), 7.76 (ddd, 1 H, J=1.7, 7.4, 8.4 Hz), 7.69 (dd, 1 H, J=1.7, 7.9 Hz), 7.38 (d, 1 H, J=8.4 Hz), 7.09 (dt, 1 H, J=1.0, 7.9 Hz), 6.48 (br s, 1 H), 6.33 (br s, 1 H), 6.26 (t, 1 H, J=2.2 Hz), 4.00 (s, 3 H), 2.15 (s, 3 H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C14H14O5S: 317.0 (M+Na). Found: 316.9

Workup

  1. customat ambient temperature
  2. customfor 3 h
  3. filtrationthen filtered through Celite with methanol
  4. customSolvent was removed in vacuo
  5. customthe crude product was purified by flash column chromatography (dichloromethane to 5% ethyl acetate in dichloromethane)

Sources & evidence

ORD record
ord-74dc9fc960cb4a569c6cd95a163bd7c4
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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