Triphenylphosphine → (3-(1,3-Dioxoisoindolin-2-yl)propyl)triphenylphosphonium bromide

HRID 2163492Notes

Reaction equation

HRID 2163492 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][N:5]1[C:9](=[O:10])[C:8]2=[CH:11][CH:12]=[CH:13][CH:14]=[C:7]2[C:6]1=[O:15].[C:16]1([P:22]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1C=CC=CC=1>[Br-:1].[C:9]1(=[O:10])[N:5]([CH2:4][CH2:3][CH2:2][P+:22]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:6](=[O:15])[C:7]2=[CH:14][CH:13]=[CH:12][CH:11]=[C:8]12

Participants

4

Reactant 2

HCID 11776TriphenylphosphineHCID 21611N-3-Bromopropylphthalimide

Product 1

HCID 22018487(3-(1,3-Dioxoisoindolin-2-yl)propyl)triphenylphosphonium bromide

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 20 mmole of N-(3-bromopropyl)phthalimide and 22 mmole of triphenylphosphine in 50 ml of benzene is heated at reflux temperature for 2 days. The solid which separates on cooling is filtered, washed with benzene and dried under reduced pressure to give 3-phthalimidopropyl triphenylphosphonium bromide. To a solution of 100 ml of dry liquid ammonia is added finely divided sodium (0.46 g or 2 × 10-2M) and a catalytic amount of ferric nitrate. When the blue sodium solution turns gray 10 g or 2 × 10-2M of finely powdered 3-phthalimidopropyltriphenylphosphonium bromide is added. After stirring for 15 minutes the ammonia is evaporated under a stream of nitrogen. To the residue is added 100 ml of anhydrous benzene and the solution is boiled for about 10 minutes under nitrogen. The solid residue is filtered pff and to the filtrate, containing salt free 3-phthalimidopropylidene triphenylphosphorane is added 6.6 g of 5 × 10-2M of ethyl trifluoroacetate. The reaction mixture is heated at reflux temperature under nitrogen for 12 hours. Concentration of the solvent leaves a residue which is distilled under high vacuum to afford 2-ethoxy-1,1,1-trifluoro-5-phthalimidopent-2ene. A solution of 3 g of 2-ethoxy-1,1,1-trifluoro-5-phthalimidopent- 2-ene in 50 ml of ether is treated with a solution of 1 M of sulfuric acid in 50 ml of water. The reaction mixture is stirred for one half hour at 25° C. The ether phase is separated, washed with brine, and dried over magnesium sulfate and concenrated to give trifluoromethyl 3-phthalimidopropyl ketone.

Workup

  1. temperatureis heated
  2. temperatureat reflux temperature for 2 days
  3. temperatureon cooling
  4. filtrationis filtered
  5. washwashed with benzene
  6. customdried under reduced pressure

Sources & evidence

ORD record
ord-22e28a3b2baa42cfa009ea82d3cc5fff
Source dataset
uspto-grants-1979_01
Patent number
US04134918

Reaction notes

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