Ethyl bromoacetate → Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester

HRID 1084478Notes

Reaction equation

HRID 1084478 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.BrCC(OCC)=O.[Br-].[CH2:28]([O:30][C:31]([CH2:33][P+:34]([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:32])[CH3:29].[PH4+].[OH-].[Na+]>C1C=CC=CC=1.O>[CH2:28]([O:30][C:31]([CH:33]=[P:34]([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)([C:41]1[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:32])[CH3:29]

Participants

8

Reactant 5

HCID 7748Ethyl bromoacetateHCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 73731(Ethoxycarbonylmethyl)triphenylphosphonium bromideHCID 5460504Phosphonium

Product 1

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterYield 80%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

Triphenyl phosphine (13 g.) was dissolved in dry benzene (60 ml.) and ethyl bromoacetate (8.3 g.) was added dropwise. The solution was heated at 70° for 2 days, and then cooled and filtered. The residue was washed with benzene and dried to give about 16 g. of (ethoxycarbonylmethyl) triphenylphosphonium bromide. The phosphonium salt (10 g.) was dissolved in water (250 ml.) and 5% aqueous sodium hydroxide was added dropwise with stirring until the solution became alkaline to litmus. The resulting precipitate was filtered off, washed with water and dried. Crystallisation from ethyl acetate/petroleum spirit gave (ethoxycarbonyl methylene) triphenyl phosphorane as a colourless solid in about 80% yield.

Workup

  1. temperatureThe solution was heated at 70° for 2 days
  2. temperaturecooled
  3. filtrationfiltered
  4. washThe residue was washed with benzene
  5. customdried
  6. customto give about 16 g
  7. filtrationThe resulting precipitate was filtered off
  8. washwashed with water
  9. customdried
  10. customCrystallisation from ethyl acetate/petroleum spirit

Sources & evidence

ORD record
ord-7fc3916a6a8746b38b77214c17098b38
Source dataset
uspto-grants-1991_04
Patent number
US05004822

Reaction notes

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