Dimethyl Sulfoxide → HCID 15382135, compound

HRID 361633Notes

Reaction equation

HRID 361633 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Si:11]([O:28][CH2:29][C@@H:30]1[C@@H:34]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][C:41]([O:43][CH:44]([CH3:46])[CH3:45])=[O:42])[C@@H:33]([OH:47])[CH2:32][O:31]1)([C:24]([CH3:27])([CH3:26])[CH3:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C>C(Cl)Cl.O>[Si:11]([O:28][CH2:29][C@@H:30]1[C@@H:34]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][C:41]([O:43][CH:44]([CH3:45])[CH3:46])=[O:42])[C:33](=[O:47])[CH2:32][O:31]1)([C:24]([CH3:26])([CH3:27])[CH3:25])([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 15382134HCID 15382134, compound

Product 1

HCID 15382135HCID 15382135, compoundYield 99.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

A dry 100 mL round-bottom flask was charged with 15 mL of anhydrous CH2Cl2 and oxalyl chloride (2.8 mL, 2.0M in CH2Cl2, 5.6 mmol) and this solution was cooled to -78° C. A solution of DMSO (0.78 mL, 11.0 mmol) in 5 mL of CH2Cl2 was added dropwise and the resulting solution was stirred for 3 min. To this mixture, a solution of the alcohol 4 (1.92 g, 3.65 mmol) in 30 mL of CH2Cl2 was added dropwise and stirring was continued for 15 min. Triethylamine (1.5 mL, 11.0 mmol) was then introduced dropwise and the mixture was allowed to warm to room temperature over 15 min. The reaction mixture was poured into 50 mL of water, the layers were separated and the aqueous layer was extracted with 50 mL of CH2Cl2. The combined organic extracts were washed with water and brine, and dried over anhydrous MgSO4. Filtration, solvent removal and chromatography of the crude on silica gel afforded the ketone 5 (1.9 g, 99% yield) as pale yellow oil: Rf 0.7 (60% EtOAc/hexane); 13C-NMR (CDCl3) δ217.04, 173.21, 135.59, 132.99, 129.83, 129.77, 127.75, 127.72, 83.48, 71.34, 67.34, 65.79, 47.87, 34.61, 29.23, 28.83, 28.29, 26.89, 26.75, 24.90, 21.84, 19.19.

Workup

  1. stirringstirring
  2. waitwas continued for 15 min
  3. temperatureto warm to room temperature over 15 min
  4. customthe layers were separated
  5. extractionthe aqueous layer was extracted with 50 mL of CH2Cl2
  6. washThe combined organic extracts were washed with water and brine
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationFiltration, solvent removal and chromatography of the crude on silica gel

Sources & evidence

ORD record
ord-1027b286eafd4b5e8cd148cc5c66f0cf
Source dataset
uspto-grants-1999_02
Patent number
US05866602

Reaction notes

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