Dimethyl Sulfoxide → HCID 11634036, compound

HRID 2380940Notes

Reaction equation

HRID 2380940 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Si:11]([O:28][CH2:29][C@@H:30]1[CH2:34][CH2:33][C@@:32]([C@@H:36]([CH3:41])/[CH:37]=[CH:38]/[CH2:39][OH:40])([CH3:35])[C:31]1([CH3:43])[CH3:42])([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[CH2:34][CH2:33][C@@:32]([C@@H:36]([CH3:41])/[CH:37]=[CH:38]/[CH:39]=[O:40])([CH3:35])[C:31]1([CH3:42])[CH3:43])([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 11496385HCID 11496385, compound

Product 1

HCID 11634036HCID 11634036, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of oxalyl chloride (0.6377 mL, 7.31 mmol) in dry CH2Cl2 (15.0 mL) was added dropwise DMSO (0.7786 mL, 10.96 mmol) at −78° C. over a period of 10 minutes and the mixture was stirred at −78° C. for 15 minutes. A solution of intermediate (12) (0.820 g, 1.83 mmol) in dry CH2Cl2 (5.0 mL) was then added dropwise at −78° C. over a period of 30 minutes and the reaction mixture was stirred at −78° C. for 30 minutes. Triethylamine (2.04 mL, 14.6 mmol) was added dropwise at −78° C. over a period of 10 minutes and the reaction mixture was stirred at −78° C. for 1 hour. The temperature of the mixture was allowed to rise to −10° C. over a period of 3.5 hours and then H2O (50 mL) was added. The organic layer was separated, the aqueous layer was extracted with diethyl ether (3×20 mL), the combined organic layers were dried over anhydrous MgSO4, and the solvent was removed under reduced pressure and the resulting residue was purified over silica (n-hexane/EtOAc, 97:3) to afford 0.776 g (92% yield) of the desired intermediate (13) which was characterized as follows:

Workup

  1. stirringthe reaction mixture was stirred at −78° C. for 30 minutes
  2. stirringthe reaction mixture was stirred at −78° C. for 1 hour
  3. waitto rise to −10° C. over a period of 3.5 hours
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted with diethyl ether (3×20 mL)
  6. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  7. customthe solvent was removed under reduced pressure
  8. customthe resulting residue was purified over silica (n-hexane/EtOAc, 97:3)

Sources & evidence

ORD record
ord-fd525d65a15942838fc8a7bceb0804fd
Source dataset
uspto-grants-2012_09
Patent number
US08258126B2

Reaction notes

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