Dimethyl Sulfoxide → HCID 11189560, compound

HRID 750471Notes

Reaction equation

HRID 750471 reaction equation
C(Cl)(C(Cl)=O)=O.CS(C)=O.[CH3:11][C:12]1([CH3:42])[O:16][C@H:15]([C@H:17]([OH:39])[CH2:18][O:19][C:20]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:14]([CH:40]=[CH2:41])[O:13]1.C(N(CC)CC)C.[Cl-].[NH4+]>C(Cl)Cl>[CH3:11][C:12]1([CH3:42])[O:16][C@H:15]([C:17](=[O:39])[CH2:18][O:19][C:20]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)([C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:14]([CH:40]=[CH2:41])[O:13]1

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 69030629HCID 69030629, compound

Product 1

HCID 11189560HCID 11189560, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a stirred solution of (COCl)2 (28.69 ml, 57.38 mmol, 2 M solution in CH2Cl2) in CH2Cl2 (200 ml) was dropwise added a solution of DMSO (8.9 ml, 125.51 mmol) in CH2Cl2 (30 ml) at −78° C., and the reaction mixture was stirred at the same temperature for 30 minutes. A solution of alcohol 3 (15.44 g, 35.86 mmol) in CH2Cl2 (30 ml) was added and the reaction mixture was stirred at −78° C. for 1 hour. Triethylamine (32.99 ml, 236.68 mmol) was added at −78° C. and then the reaction mixture was allowed to warm to room temperature and stirred for 1 hour. A saturated ammonium chloride solution was added carefully at 0° C. and the reaction mixture partitioned between CH2Cl2 and water. The organic layer was dried, filtered, and evaporated under reduced pressure. The residue was purified by silica gel column chromatography using hexane and ethyl acetate (6:1) to give ketone 4 (13.83 g, 90%) as a white solid; 1H NMR (400 MHz, CDCl3) δ 7.46-7.23 (m, 15H), 5.56 (ddd, J=17.2, 10.4, 6.8 Hz, 1H), 5.26 (td, J=16.8, 1.2 Hz, 1H), 5.13 (td, J=10.4, 1.2 Hz, 1H), 4.88-4.84 (m, 1H), 4.76 (d, J=7.6 Hz, 1H), 4.06 (d, J=18.0 Hz, 1H), 3.72 (d, J=18.4 Hz, 1H), 1.41 (s, 3H), 1.34 (s, 3H).

Workup

  1. stirringthe reaction mixture was stirred at −78° C. for 1 hour
  2. stirringstirred for 1 hour
  3. customthe reaction mixture partitioned between CH2Cl2 and water
  4. customThe organic layer was dried
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-c66443829f7546de965a106414931c5a
Source dataset
uspto-grants-2008_07
Patent number
US07405214B2

Reaction notes

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