Dimethyl Sulfoxide → HCID 58527611, compound

HRID 868901Notes

Reaction equation

HRID 868901 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH2:11]([O:18][C@@H:19]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH2:20][OH:21])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CCN(CC)CC>C(Cl)Cl.CCOCC.O>[CH2:11]([O:18][C@@H:19]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH:20]=[O:21])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chloride2×HCID 12201883(S)-2-(benzyloxy)dodecan-1-ol

Product 1

HCID 58527611HCID 58527611, compoundYield 67%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent3×

Procedure

CH2Cl2 (10 mL) and oxalyl chloride (1.72 mL, 20.3 mmol) were added to an oven-dried 2-neck round bottom flask containing a magnetic stir bar under Ar. The flask was immersed in a dry ice/acetone bath. A solution of DMSO (2.88 mL, 40.6 mmol) in CH2Cl2 (10 mL) was added to the stirred solution of oxalyl chloride slowly. 403 (5.4 g, 18.5 mmol) was dissolved in CH2Cl2 and added dropwise, over a period of 15 minutes, to the cold, stirred reaction mixture. After stirring for 2 hours, Et3N (12.9 mL, 18.46 mmol) was added to the reaction mixture, which was then allowed to warm to room temperature. The mixture was diluted with Et2O (˜300 mL) and water. The ether layer was washed with sat. aq. NaHCO3, 1M aq. HCl, and brine. The Et2O layer was then dried over MgSO4, filtered through paper, and concentrated by rotary evaporation. The crude product was purified by chromatography on silica (gradient elution from hexanes to 1:1 EtOAc/hexanes); fractions containing the desired product were pooled and concentrated affording 404 (3.58 g, 67%) as a clear, slightly viscous oil. 1H NMR (400 MHz, CDCl3): δ 9.66 (d, J=1.9 Hz, 1 H), 7.37-7.31 (m, 5H), 4.69 (d, J=11.7 Hz, 1H), 4.55 (d, J=11.7 Hz, 1H), 3.78-3.75 (m, 1 H), 1.68 (dd, J=14.3, 7.2 Hz, 2H), 1.49-1.35 (m, 2H), 1.25 (br s, 14H), 0.89 (t, J=6.7, 3H)

Workup

  1. additioncontaining a magnetic stir bar under Ar
  2. customThe flask was immersed in a dry ice/acetone bath
  3. additionadded dropwise, over a period of 15 minutes, to the cold
  4. customreaction mixture
  5. stirringAfter stirring for 2 hours
  6. washThe ether layer was washed with sat. aq. NaHCO3, 1M aq. HCl, and brine
  7. dry with materialThe Et2O layer was then dried over MgSO4
  8. filtrationfiltered through paper
  9. concentrationconcentrated by rotary evaporation
  10. customThe crude product was purified by chromatography on silica (gradient elution from hexanes to 1:1 EtOAc/hexanes)
  11. additionfractions containing the desired product
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-72f2ba65115e4e9d924cdf79a0690f99
Source dataset
uspto-grants-2015_03
Patent number
US08969353B2

Reaction notes

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