Triphenylphosphonium bromide → 3-Phenyl-3-cyclopentenecarboxylic acid

HRID 1654694Notes

Reaction equation

HRID 1654694 reaction equation
[C:1]([CH2:9][CH:10]1[CH2:14][CH2:13][O:12][C:11]1=[O:15])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C2CC(C(O)=O)CCC=2)C=CC=CC=1>CS(C)=O.O1CCCC1>[C:2]1([C:1]2[CH2:9][CH:10]([C:11]([OH:12])=[O:15])[CH2:14][CH:13]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 80811Triphenylphosphonium bromideHCID 117889393-(benzoylmethyl)-4,5-dihydro-2(3H)-furanoneHCID 156418093-Phenyl 3 cyclohexenecarboxylic acid

Product 1

HCID 200766803-Phenyl-3-cyclopentenecarboxylic acidYield 67.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
170 °C

Procedure

3-(Benzoylmethyl)-4,5-dihydro-2(3H)-furanone (5.00 g, Step A) and triphenylphosphine hydrobromide (8.41 g) are mixed and heated to 170° C. in an oil bath under nitrogen for 1 hour. The mixture is cooled and powdered. The powder is dissolved in dimethylsulfoxide (50 mL) and diluted with tetrahydrofuran (30 mL). The solution is stirred under nitrogen and cooled in an ice-bath. Dimsyl sodium (25 mL of 2M, see Example D, Step C) is added dropwise over 20 minutes keeping the internal temperature below 14° C. The mixture is stirred at 25° C. for 2 hours and the solvents evaporated. The residue is treated with water (80 mL) containing saturated aqueous sodium bicarbonate (10 mL) and extracted with dichloromethane (3×50 mL). The extracts are washed with dilute aqueous sodium bicarbonate. The aqueous layers are washed with dichloromethane (30 mL) and acidified with concentrated hydrochloric acid. The aqueous layers are extracted with dichloromethane (3×50 mL), the extracts dried over magnesium sulfate, filtered, and evaporated to a brown oil. The oil is washed through silica gel (30 g) with 2:1 chloroform:ethyl acetate to give 3.1 g of 3-phenyl-3-cyclopentenecarboxylic acid as a brown solid.

Workup

  1. temperatureThe mixture is cooled
  2. temperaturecooled in an ice-bath
  3. customthe internal temperature below 14° C
  4. stirringThe mixture is stirred at 25° C. for 2 hours
  5. customthe solvents evaporated
  6. additionThe residue is treated with water (80 mL)
  7. additioncontaining saturated aqueous sodium bicarbonate (10 mL)
  8. extractionextracted with dichloromethane (3×50 mL)
  9. washThe extracts are washed with dilute aqueous sodium bicarbonate
  10. washThe aqueous layers are washed with dichloromethane (30 mL)
  11. extractionThe aqueous layers are extracted with dichloromethane (3×50 mL)
  12. dry with materialthe extracts dried over magnesium sulfate
  13. filtrationfiltered
  14. customevaporated to a brown oil
  15. washThe oil is washed through silica gel (30 g) with 2:1 chloroform

Sources & evidence

ORD record
ord-31238941e13f4774a15e0905aef63540
Source dataset
uspto-grants-1995_04
Patent number
US05409931

Reaction notes

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