Triphenylphosphine → Triphenylphosphine Oxide

HRID 1060564Notes

Reaction equation

HRID 1060564 reaction equation
C[O:2]C(=O)C1C=CC=C(O)C=1.[C:12]1([P:18]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1>[C:25]1([P:18](=[O:2])([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 88068Methyl 3-HydroxybenzoateHCID 5462977Diethyl azodicarboxylate

Product 1

HCID 13097Triphenylphosphine Oxide

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a well-stirred solution consisting of (7S,9aS)-cis-(2-Benzo[d]isoxazol-3-yl-octahydro-pyrido[1,2-a]pyrazin-7-yl)-methanol (3.40 g, 11.83 mmol), methyl-3-hydroxybenzoate (2.70 g, 17.75 mmol), and triphenylphosphine (3.70 g, 14.20 mmol), in anhydrous tetrahydrofuran (68 ml), diethylazodicarboxylate (2.24 ml, 14.20 mmol) was added. The resulting solution was heated at 50° C. for 2 hours. The solvent was removed in vacuo, and the resulting residue was extracted into a biphasic 1N aqueous sodium hydroxide (40 ml)/methylene chloride (50 ml) mixture. The aqueous phase was twice extracted with equal volume portions of fresh methylene chloride. The combined organic extracts were dried (anhydrous magnesium sulfate), and concentrated to an amber oil. An initial flash chromatography (silica gel, 70-230 micron mesh; elution with methanol/methylene chloride=1:99 in volume) afforded partially purified product (3.3 g, contaminants: hydrazine diethylcarboxylate and triphenylphosphine oxide). A second flash chromatography of the entire sample (silica gel, 230-400 micron mesh, elution with methanol/methylene chloride=1:99) afforded the purified title compound (1.37 g, 27% yield) as a colorless amorphous solid.

Workup

  1. customThe solvent was removed in vacuo
  2. extractionthe resulting residue was extracted into a biphasic 1N aqueous sodium hydroxide (40 ml)/methylene chloride (50 ml) mixture
  3. extractionThe aqueous phase was twice extracted with equal volume portions of fresh methylene chloride
  4. dry with materialThe combined organic extracts were dried (anhydrous magnesium sulfate)
  5. concentrationconcentrated to an amber oil
  6. washAn initial flash chromatography (silica gel, 70-230 micron mesh; elution with methanol/methylene chloride=1:99 in volume)

Sources & evidence

ORD record
ord-28bea0551d55419da467c605f28f539e
Source dataset
uspto-grants-2003_02
Patent number
US06525048B1

Reaction notes

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