Dimethyl Sulfoxide → HCID 53938517, compound

HRID 442981Notes

Reaction equation

HRID 442981 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([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:5]=[CH:6][CH:7]=1.C(N(CC)C(C)C)(C)C.CS(C)=O>ClCCl>[Br:1][C:2]1[CH:3]=[C:4]([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:10])=[O:9])[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 81531DiisopropylethylamineHCID 54004475HCID 54004475, compound

Product 1

HCID 53938517HCID 53938517, compoundYield 68.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a cooled (0° C.), stirred solution of 914 mg (2.28 mmol) 3-[3-(3-bromophenylsulfonyloxy)-5-methylphenoxy]propanol, as prepared in the preceding step, 795 μL of N,N-diisopropylethylamine and 485 μL of anhydrous dimethyl sulfoxide in 15 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 3 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 brine (25 mL) and dried over Na2SO4 to give, after concentration, a white semisolid. This material was chromatographed on 80 g of silica gel with 3% ethyl acetate-dichloromethane to afford 620 mg (68%) of the title compound as a colorless oil: 1H-NMR (300 MHz; CDCl3) δ 9.84 (t, 1H, J=1.4 Hz), 8.01 (t, 1H, J=1.8 Hz), 7.79 (m, 2H), 7.43 (t, 1H, J=8.0 Hz), 6.64 (m, 1H), 6.44 (m, 1H), 6.37 (t, 1H, J=2.0 Hz), 4.20 (t, 2H, J=6.1 Hz), 2.87 (td, 2H, J=6.1, 1.4 Hz) and 2.26 (s, 3H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C16H15BrO5S: 423.0 (M+2+Na, 81Br ion). Found: 423.1.

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. washwashed with 5% (w/v) aqueous citric acid (2×25 mL)
  4. extractionEach wash was extracted with 5 mL of dichloromethane
  5. washthe combined extracts were washed with brine (25 mL)
  6. dry with materialdried over Na2SO4
  7. customto give
  8. concentrationafter concentration
  9. customThis material was chromatographed on 80 g of silica gel with 3% ethyl acetate-dichloromethane

Sources & evidence

ORD record
ord-02f8036c71d845c2af50feac38fe73fa
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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