Sodium Hydroxide → 2-(6-Carboxy-2-cis-hexenyl)cyclopent-2-en-1-one

HRID 1903973Notes

Reaction equation

HRID 1903973 reaction equation
[H-].[Na+].[Br-].[C:4]([CH2:7][CH2:8][CH2:9][CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([OH:6])=[O:5].[CH:30]([CH2:32][C:33]1[C:34](=[O:38])[CH2:35][CH2:36][CH:37]=1)=O.[OH-].[Na+]>CS(C)=O>[C:4]([CH2:7][CH2:8][CH2:9][CH2:10]/[CH:30]=[CH:32]\[C:33]1[C:34](=[O:38])[CH2:35][CH2:36][CH:37]=1)([OH:6])=[O:5]

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 20465672(5-Oxocyclopent-1-en-1-yl)acetaldehyde

Product 1

HCID 867329642-(6-Carboxy-2-cis-hexenyl)cyclopent-2-en-1-one

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Procedure

A mixture of 0.194 g. (0.007952 mole) of sodium hydride (free of mineral oil) and 5.5 ml. of dimethylsulfoxide is heated to 70° C. until gas evolution ceases under a nitrogen atmosphere. The resulting solution is cooled below room temperature, and treated with a solution of 1.400 g. (0.00316 mole) of 4-carboxybutyltriphenyl phosphonium bromide [E. J. Corey et al., J. Am. Chem. Soc., 91, 5675 (1969)] in 6 ml. of dimethylsulfoxide. To the resulting red solution is added 0.00263 mole of 2-formylmethylcyclopent-2-en-1-one (Example 898) in 2 ml. of dimethylsulfoxide and the mixture is stirred at room temperature for 2.25 hours. The mixture is poured into ice water, sodium hydroxide solution is added to pH 12, and the neutral materials are extracted with diethyl ether. The basic phase is acidified with dilute hydrochloric acid and in extracted with diethyl ether. The organic phase is washed with water and saturated brine, dried (Na2SO4), and evaporated to a semicrystalline mass. The latter is triturated with hot hexane, the solids are filtered off, and the filtrate is evaporated to yield the subject product as an oil.

Workup

  1. additionA mixture of 0.194 g
  2. temperatureThe resulting solution is cooled below room temperature
  3. additiontreated with a solution of 1.400 g
  4. additionis added to pH 12
  5. extractionthe neutral materials are extracted with diethyl ether
  6. extractionin extracted with diethyl ether
  7. washThe organic phase is washed with water and saturated brine
  8. dry with materialdried (Na2SO4)
  9. customevaporated to a semicrystalline mass
  10. customThe latter is triturated with hot hexane
  11. filtrationthe solids are filtered off
  12. customthe filtrate is evaporated

Sources & evidence

ORD record
ord-7de1e6962ef9451fbb8e934cfe14b484
Source dataset
uspto-grants-1984_03
Patent number
US04439365

Reaction notes

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