Acetic Acid → Triphenylphosphine Oxide

HRID 652751Notes

Reaction equation

HRID 652751 reaction equation
[Cl-].COC[P+:5]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(OC)(=[O:31])CCCC=CC.C(O)(=O)C.[NH4+].[Cl-]>C1(C)C=CC=CC=1.CCOCC>[C:6]1([P:5](=[O:31])([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 25517Ammonium ChlorideHCID 5540505-Heptenoic acid, methyl esterHCID 2723798Methoxymethyl-triphenylphosphonium chloride

Product 1

HCID 13097Triphenylphosphine Oxide

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried methoxymethyltriphenylphosphonium chloride ((C6H5)3P+ --CH2OCH3Cl-) (12.9 g, 37.7 mmol) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which is stirred at 0° C. for an additional 35 minutes. Thereafter, a solution of 4.8 g (18.8 mmol) of [1β,2α(5Z),3α,4β]-7-(3-formyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) of acetic acid in 5 ml ether. The mixture is immediately poured into 200 ml saturated NH4Cl, and extracted with ether (4×200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4 anhydrous) and concentrated to yield a yellow oil in a white crystalline solid (triphenylphosphine oxide). This is washed with EtOAc and the material in the washings is purified by chromatography on an LPS-1 silica gel column. The fractions obtained are (A) [1α,2β(5Z), 3β,4α]-7-[[3-(2-oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1α,2β(5Z),3β,4α]-7-[3-(2-methoxy)ethendiyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1α,2β(5Z),3β,4α]-7-[[3-(2,2-dimethoxy)ethyl]-7-oxabicylo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Workup

  1. additionInto a dry 100 ml round bottom 3-necked flask containing a stir bar
  2. distillationdistilled toluene (stored over molecular sieves)
  3. customA bright red solution formed which
  4. stirringis stirred at 0° C. for an additional 35 minutes
  5. extractionextracted with ether (4×200 ml)
  6. washThe combined ether phases are washed with NaCl saturated solution
  7. dry with materialdried (MgSO4 anhydrous)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-c6480aadb50240e2af11d8680853acfd
Source dataset
uspto-grants-1987_06
Patent number
US04673685

Reaction notes

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