Tributylphosphine → Trioctylphosphine

HRID 1871660Notes

Reaction equation

HRID 1871660 reaction equation
C([O-])=O.[NH4+].[CH2:5]([P:9]([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:10][CH2:11][CH2:12][CH3:13])[CH2:6][CH2:7][CH3:8]>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:14]([P:9]([CH2:5][CH2:6][CH2:7][CH2:8][CH2:8][CH2:7][CH2:6][CH3:5])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:17][CH2:16][CH2:15][CH3:14])[CH2:15][CH2:16][CH2:17][CH2:10][CH2:11][CH2:12][CH3:13]

Participants

5

Reactant 2

HCID 13831TributylphosphineHCID 2723923Ammonium formate

Product 1

HCID 20851TrioctylphosphineYield 62%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

EpB (30.0 mL), ammonium formate (24 g), tris(dibenzylideneacetone)dipalladium(0) (0.15 g) and tributylphosphine (0.50 mL) were added to 50 mL of THF solvent. This mixture was stirred at reflux for 1 hour and then filtered through silica gel to remove the palladium catalyst. The product was analyzed by GC and found to be nearly identical to the product obtained in Comparative Example 1 using trioctylphosphine, which consisted of 3-buten-1-ol/2-buten-1-ol in a mole ratio of >98:2), a small amount of crotonaldehyde, and a large amount of high boilers. This product was distilled through a Vigreux column to afford a product cut with 97.2% selectivity. The isolated yield was 62%. Formation of a white solid during this reaction resulted in a pressure buildup and a vapor release.

Workup

  1. temperatureat reflux for 1 hour
  2. filtrationfiltered through silica gel
  3. customto remove the palladium catalyst

Sources & evidence

ORD record
ord-2893ecb446784a5d9be75473f1b38684
Source dataset
uspto-grants-2000_08
Patent number
US06103943

Reaction notes

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