Dimethyl Sulfoxide → HCID 14499627, compound

HRID 1199731Notes

Reaction equation

HRID 1199731 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[F:11][CH2:12][CH:13]([N:18]1[C:22](=[O:23])[C:21]2=[CH:24][CH:25]=[CH:26][CH:27]=[C:20]2[C:19]1=[O:28])[CH2:14][CH2:15][CH2:16][OH:17].C(N(CC)CC)C>ClCCl.O>[F:11][CH2:12][CH:13]([N:18]1[C:19](=[O:28])[C:20]2=[CH:27][CH:26]=[CH:25][CH:24]=[C:21]2[C:22]1=[O:23])[CH2:14][CH2:15][CH:16]=[O:17]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 14499626HCID 14499626, compound

Product 1

HCID 14499627HCID 14499627, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent4×

Conditions

Temperature
-60 °C

Procedure

To a solution at -60° C. of oxalylchloride (75.3 g, 0.59 mol) in dry dichloromethane (2 L) under nitrogen, was added a solution of dry DMSO (89.1 g, 1.14 mol) in dry dichloromethane (2 L). 5-Fluoro-4-phthalimidopentanol, 5a, (R=--CH2F) (135 g, 0.54 mol) in CH2Cl2 (2 L) was then added over 15 min. The mixture was stirred 45 min. at -60° C., a solution of triethylamine (352 g, 3.47 mol) in dry CH2Cl2 (2 L) was added slowly (exothermic). The solution was stirred overnight, cooled to -10° C. and water (2 L) added. The organic phase was separated, washed with 4 N HCl, followed by water (3×2 L). The organic phase was separated, dried over Na2SO4 and evaporated. The residue was dissolved in ether, washed with water (3×0.5 L) and dried over Na2SO4. Evaporation of the ether phase gave an oil which was heated at 70° C./0.1 mm Hg to remove traces of DMSO. The title compound (6, R=--CH2F) was obtained as a red oil: 136 g (100%). NMR (1H, CDCl3, 90 MHz).

Workup

  1. stirringThe solution was stirred overnight
  2. temperaturecooled to -10° C.
  3. customThe organic phase was separated
  4. washwashed with 4 N HCl
  5. customThe organic phase was separated
  6. dry with materialdried over Na2SO4
  7. customevaporated
  8. dissolutionThe residue was dissolved in ether
  9. washwashed with water (3×0.5 L)
  10. dry with materialdried over Na2SO4
  11. customEvaporation of the ether phase
  12. customgave an oil which
  13. temperaturewas heated at 70° C./0.1 mm Hg
  14. customto remove traces of DMSO

Sources & evidence

ORD record
ord-57eb90ad7d3647c2ade7e263e19b9465
Source dataset
uspto-grants-1990_02
Patent number
US04902719

Reaction notes

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