Dimethyl Sulfoxide → 3-(2-Methoxyphenylsulfonyloxy)-5-methylphenoxyacetaldehyde

HRID 442961Notes

Reaction equation

HRID 442961 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[S:9]([O:12][C:13]1[CH:14]=[C:15]([CH:20]=[C:21]([CH3:23])[CH:22]=1)[O:16][CH2:17][CH2:18][OH:19])(=[O:11])=[O:10].C(N(CC)C(C)C)(C)C.CS(C)=O>ClCCl>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[S:9]([O:12][C:13]1[CH:14]=[C:15]([CH:20]=[C:21]([CH3:23])[CH:22]=1)[O:16][CH2:17][CH:18]=[O:19])(=[O:11])=[O:10]

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 81531DiisopropylethylamineHCID 541437062-[3-(2-Methoxyphenylsulfonyloxy)-5-methylphenoxy]ethanol

Product 1

HCID 539480863-(2-Methoxyphenylsulfonyloxy)-5-methylphenoxyacetaldehydeYield 61%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-[3-(2-methoxyphenylsulfonyloxy)-5-methylphenoxy]-ethanol (322 mg, 0.95 mmol, as prepared in the preceding step), N,N-diisopropylethylamine (0.35 mL, 2.0 mmol), anhydrous dimethyl sulfoxide (0.20 mL, 2.9 mmol) and anhydrous dichloromethane (2.5 mL) was cooled to 0° C. under nitrogen. Sulfur trioxide pyridine complex (308 mg, 1.9 mmol) was added in portions over 10 minutes. The solution was stirred at 0° C. for 5 hours, then the reaction was quenched with 5% aqueous citric acid (25 mL). Diethyl ether (25 mL) was added, and the mixture was extracted. The aqueous layer was extracted with diethyl ether (25 mL), and the combined organic layers were washed with 5% aqueous citric acid (25 mL). The aqueous layer was extracted with diethyl ether (25 mL), and the combined organic layers were washed with pH 7 buffer (0.5M, 2×40 mL) and brine (40 mL). The organic layer was dried over Na2SO4, filtered, and concentrated to an oil. Crude product was purified by flash column chromatography through silica gel (0% to 5% acetone in dichloromethane) to give the title compound as a colorless oil (195 mg, 61%). 1H-NMR (300 MHz, CDCl3) δ 9.76 (t, 1H, J=1 Hz), 7.81 (dd, 1H, J=1.7, 7.9 Hz), 7.60-7.65 (m, 1H), 7.09 (d, 1H, J=8 Hz), 7.00-7.05 (m, 1H), 6.63 (br s, 1H), 6.59 (br s, 1H), 6.41 (t, 1H, J=2.2 Hz), 4.45 (d, 2H, J=1 Hz), 4.03 (s, 3H), 2.27 (s, 3H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C16H16O6S: 359.1 (M+Na). Found: 358.8.

Workup

  1. additionSulfur trioxide pyridine complex (308 mg, 1.9 mmol) was added in portions over 10 minutes
  2. customthe reaction was quenched with 5% aqueous citric acid (25 mL)
  3. additionDiethyl ether (25 mL) was added
  4. extractionthe mixture was extracted
  5. extractionThe aqueous layer was extracted with diethyl ether (25 mL)
  6. washthe combined organic layers were washed with 5% aqueous citric acid (25 mL)
  7. extractionThe aqueous layer was extracted with diethyl ether (25 mL)
  8. washthe combined organic layers were washed with pH 7 buffer (0.5M, 2×40 mL) and brine (40 mL)
  9. dry with materialThe organic layer was dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated to an oil
  12. customCrude product was purified by flash column chromatography through silica gel (0% to 5% acetone in dichloromethane)

Sources & evidence

ORD record
ord-45342c6e43394608a367f31be4d3634a
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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