Triphenylphosphine → HCID 58400533, compound

HRID 2382210Notes

Reaction equation

HRID 2382210 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[OH:9].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:29][C:30]1([CH3:39])[O:34][C@@H:33]([CH:35](O)[CH:36]=[CH2:37])[CH2:32][O:31]1>C1COCC1>[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[O:9][CH:35]([C@H:33]1[CH2:32][O:31][C:30]([CH3:39])([CH3:29])[O:34]1)[CH:36]=[CH2:37]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 6054722-Bromo-4-fluorophenolHCID 10920779HCID 10920779, compound

Product 1

HCID 58400533HCID 58400533, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

On a stirred solution composed by 2-bromo-4-fluoro-phenol (12.07 g, 0.063 mol) and triphenylphosphine (16.18 g, 0.063 mol) in THF (85 ml) under nitrogen at 18° C., 1-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-prop-2-en-1-ol (10.0 g, 0.054 mol) was added as a crude product. The reaction mixture was then cooled to 0° C. and diisopropyl-aza-dicarboxylate (12.78 g, 0.063 mol) was added dropwise over a period of 30 min. At the end of the addition the temperature was raised gradually to 18° C. and the mixture left to stir for further 1 h. The crude reaction was then concentrated under reduced pressure and then MTBE (31 g) added. After 15 min agitation, the slurry was filtered and the panel washed with MTBE (2×10 g). The mother liquors were then concentrated in vacuo and heptane (23 g) added. After 30 min stirring, the slurry was filtered and the cake washed with heptane (11 g). The mother liquors were then concentrated in vacuo and purified by column chomatography on silica using a mixture heptan:ethyl acetate:triethylamine 9.5:0.5:0.01, as eluent. 14.28 g of (R)-4-(1-(2-bromo-4-fluorophenoxy)allyl)-2,2-dimethyl-1,3-dioxolane were isolated as a mixture of diastereoisomers (80% yield).

Workup

  1. additionAt the end of the addition the temperature
  2. temperaturewas raised gradually to 18° C.
  3. waitthe mixture left
  4. customThe crude reaction
  5. concentrationwas then concentrated under reduced pressure
  6. additionMTBE (31 g) added
  7. waitAfter 15 min agitation
  8. filtrationthe slurry was filtered
  9. washthe panel washed with MTBE (2×10 g)
  10. concentrationThe mother liquors were then concentrated in vacuo and heptane (23 g)
  11. additionadded
  12. stirringAfter 30 min stirring
  13. filtrationthe slurry was filtered
  14. washthe cake washed with heptane (11 g)
  15. concentrationThe mother liquors were then concentrated in vacuo
  16. custompurified by column chomatography on silica using a mixture heptan:ethyl acetate:triethylamine 9.5:0.5:0.01

Sources & evidence

ORD record
ord-43180236e1de4f0ab193a1c33a08d49e
Source dataset
uspto-grants-2012_09
Patent number
US08258323B2

Reaction notes

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