Triphenylphosphine → Methyl 3-(benzyloxy)-5-(1,3-difluoropropan-2-yloxy)benzoate

HRID 1990157Notes

Reaction equation

HRID 1990157 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[OH:15][C:16]1[CH:17]=[C:18]([CH:23]=[C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20].[F:34][CH2:35][CH:36](O)[CH2:37][F:38].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[F:34][CH2:35][CH:36]([O:15][C:16]1[CH:17]=[C:18]([CH:23]=[C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20])[CH2:37][F:38]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 679851,3-Difluoro-2-propanolHCID 5363146Diisopropyl azodicarboxylateHCID 7472028Methyl 3-(benzyloxy)-5-hydroxybenzoate

Product 1

HCID 59127098Methyl 3-(benzyloxy)-5-(1,3-difluoropropan-2-yloxy)benzoateYield 113.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

DIAD (7.63 mL, 38.7 mmol) was added in a dropwise fashion to a solution of methyl 3-hydroxy-5-{[phenylmethyl]oxy}benzoate (5.00 g, 19.4 mmol), 1,3-difluoropropane-2-ol (3 mL, 38.7 mmol), and triphenylphosphine (10.16 g, 38.7 mmol) in THF (100 mL) under an inert atmosphere at 0° C. The solution was allowed to reach RT and left to stir for 2 days. The THF was removed in vacuo and the residual oil slurried with a mixture of 20% ethyl acetate in isohexane. After allowing to stir for 90 minutes the mixture was filtered and the filtrate evaporated. The residual was oil chromatographed on silica, eluting with 30% ethyl acetate in isohexane, to give the desired compound (7.41 g).

Workup

  1. customto reach RT
  2. waitleft
  3. customThe THF was removed in vacuo
  4. additionthe residual oil slurried with a mixture of 20% ethyl acetate in isohexane
  5. stirringto stir for 90 minutes the mixture
  6. filtrationwas filtered
  7. customthe filtrate evaporated
  8. customchromatographed on silica
  9. washeluting with 30% ethyl acetate in isohexane

Sources & evidence

ORD record
ord-b5af4a5a5e414314817bcdec67e0bfdd
Source dataset
uspto-grants-2010_01
Patent number
US07642259B2

Reaction notes

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