Dimethylformamide → HCID 67278503, compound

HRID 1693686Notes

Reaction equation

HRID 1693686 reaction equation
[F:1][C:2]1[CH:12]=[CH:11]C(O[C@H](C)CO)=[CH:4][CH:3]=1.[C:13]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:18]=CC=C[CH:14]=1.[Br:32]Br.C(OCC)(=O)C.CN(C)[CH:42]=[O:43]>>[Br:32][C@@H:14]([O:43][C:42]1[CH:4]=[CH:3][C:2]([F:1])=[CH:12][CH:11]=1)[CH2:13][CH3:18]

Participants

6

Reactant 5

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 11776TriphenylphosphineHCID 24408BromineHCID 13831435HCID 13831435, compound

Product 1

HCID 67278503HCID 67278503, compoundYield 74%

Conditions

Temperature
22 °C

Procedure

149 g (0.875 mol) of 4 and 97.2 g (0.875 mol) of triphenylphosphine (TPP) dissolved in 300 mL of dimethylformamide (DMF) maintained under argon at 22° C., to which was added dropwise 159.8 g (0.875 mol) of bromine. The mixture was stirred for 24 hrs. 2.5 L of ethyl acetate was then added to the reaction mixture and, after stirring an additional one hour, the organic layer was washed with 4×800 mL of water, 1 L saturated NaHCO3, and 700 mL brine. The organic layer was dried over MgSO4, filtered and concentrated in vacuo. The residue was dissolved in 1.5 L of hexane, stirred at 10° C. 2 hrs, and filtered. High vacuum distillation gave the product 5 in 74% yield (151 g). HPLC retention time 9.1 min, Bp 72-74° C. at 0.25 mm Hg. The reaction is shown as follows:

Workup

  1. stirringafter stirring an additional one hour
  2. washthe organic layer was washed with 4×800 mL of water, 1 L saturated NaHCO3, and 700 mL brine
  3. dry with materialThe organic layer was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. dissolutionThe residue was dissolved in 1.5 L of hexane
  7. stirringstirred at 10° C
  8. filtration2 hrs, and filtered
  9. distillationHigh vacuum distillation

Sources & evidence

ORD record
ord-caa69d4cb10e4aa2a12403917f9dc7a4
Source dataset
uspto-grants-2012_04
Patent number
US08158667B2

Reaction notes

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