Dimethyl Sulfoxide → HCID 53645136, compound

HRID 442918Notes

Reaction equation

HRID 442918 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:24][CH3:25])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([CH:20]=[C:21]([CH3:23])[CH:22]=2)[O:15][CH2:16][CH2:17][CH2:18][OH:19])(=[O:10])=[O:9])[CH:7]=1.C(N(CC)C(C)C)(C)C.CS(C)=O>ClCCl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:24][CH3:25])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([CH:20]=[C:21]([CH3:23])[CH:22]=2)[O:15][CH2:16][CH2:17][CH:18]=[O:19])(=[O:9])=[O:10])[CH:7]=1

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 81531DiisopropylethylamineHCID 53942355HCID 53942355, compound

Product 1

HCID 53645136HCID 53645136, compoundYield 69.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a cooled (0° C), stirred solution of 990 mg (2.30 mmol) 3-[3-(5-bromo-2-methoxyphenylsulfonyloxy)-5-methylphenoxy]propanol, as prepared in the preceding step, 842 μL of N,N-diisopropylethylamine and 500 μL of anhydrous dimethyl sulfoxide in 6.0 mL of anhydrous dichloromethane was added 732 mg (4.60 mmol) of sulfur trioxide pyridine complex. The mixture was warmed to ambient temperature over 30 min and stirred for 2 h. An additional 368 mg (2.30 mmol) of sulfur trioxide pyridine complex was added and, after 17 h, the mixture was poured into 15 mL of dichloromethane and washed with 5% (w/v) aqueous citric acid (2×25 mL). Each wash was extracted with 5 mL of dichloromethane and the combined extracts were washed with 1M pH 7 buffer (25 mL), brine (25 mL) and dried over Na2SO4 to give after concentration a white semisolid. This material was chromatographed on 35 g of silica gel with dichloromethane followed by 3% ethyl acetate-dichloromethane to afford 685 mg (69%) of the title compound as a colorless syrup: 1H-NMR (300 MHz; CDCl3) δ 9.84 (t, 1 H, J=1.4 Hz), 7.94 (d, 1 H, J=2.5 Hz), 7.70 (dd, 1 H, J=8.9, 2.5 Hz), 6.98 (d, 1 H, J=8.9 Hz), 6.61 (br s, 1 H), 6.55 (br s, 1 H), 6.45 (t, 1 H, J=2.2 Hz), 4.21 (t, 2 H, J=6.1 Hz), 4.01 (s, 3 H), 2.88 (td, 2 H, J=6.1, 1.4 Hz) and 2.27 (s, 3 H). Mass spectrum (MALDI-TOF, gentisic acid matrix) calcd. for C17H1779BrO6S: 451.0 (M+Na). Found: 451.4.

Workup

  1. additionwas added 732 mg (4.60 mmol) of sulfur trioxide pyridine complex
  2. temperatureThe mixture was warmed to ambient temperature over 30 min
  3. additionAn additional 368 mg (2.30 mmol) of sulfur trioxide pyridine complex was added and, after 17 h
  4. washwashed with 5% (w/v) aqueous citric acid (2×25 mL)
  5. extractionEach wash was extracted with 5 mL of dichloromethane
  6. washthe combined extracts were washed with 1M pH 7 buffer (25 mL), brine (25 mL)
  7. dry with materialdried over Na2SO4
  8. customto give
  9. concentrationafter concentration a white semisolid
  10. customThis material was chromatographed on 35 g of silica gel with dichloromethane

Sources & evidence

ORD record
ord-9755acc8ec164b608807b46de4a1b080
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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