Sodium hydride → HCID 54277596, compound

HRID 1578815Notes

Reaction equation

HRID 1578815 reaction equation
[H-].[Na+].[C:3]([CH2:8][C:9](OCC)=O)(=[O:7])[CH:4]([CH3:6])[CH3:5].Br[CH2:15][C:16](C)=[CH:17][CH2:18][CH2:19][C:20]([CH3:27])=[CH:21][CH2:22][O:23]C(=O)C>CCOCC>[CH3:27][C:20]([CH2:19][CH2:18][CH:17]=[C:16]([CH3:15])[CH2:9][CH2:8][C:3](=[O:7])[CH:4]([CH3:5])[CH3:6])=[CH:21][CH2:22][OH:23]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 81583Ethyl isobutyrylacetateHCID 54451904HCID 54451904, compound

Product 1

HCID 54277596HCID 54277596, compoundYield 89.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a suspension of sodium hydride (1.9 g) in ether (40 ml) while cooling with ice, ethyl isobutyroylacetate (5.2 g) is added, and 1-bromo-8-acetoxy-2,6-dimethyl-2,6-octadiene (8 g) is dropwise added thereto. The reaction is carried out with reflux for 8 hours. The ether layer is separated from the reaction mixture, washed with water, dried and evaporated. The oily product (9.9 g) is added to a solution of potassium hydroxide (6.3 g) ethanol (120 g), and refluxing is continued for about 1 hour. The resultant mixture is added to the ice water, made acidic with 10% sulfuric acid and extracted with ether. The ether extract is washed with saturated aqueous solution of sodium chloride, aqueous solution of sodium hydrogen carbonate and water in order, and then the ether is evaporated therefrom. The residue (7.2 g) is dissolved in benzene and purified by chromatography on silica gel to give 3,7,11,-trimethyl-2,6-dodecadien-10-on-1-ol (6.2 g). NMR (carbon tetrachloride): δ 1.05 (d), 1.59 (s), 2.0 (s), 21.-2.7 (m), 3.52 (s), 3.95 (d), 4.8-5.4 (m).

Workup

  1. additionis added
  2. temperaturewith reflux for 8 hours
  3. customThe ether layer is separated from the reaction mixture
  4. washwashed with water
  5. customdried
  6. customevaporated
  7. additionThe oily product (9.9 g) is added to a solution of potassium hydroxide (6.3 g) ethanol (120 g)
  8. temperaturerefluxing
  9. additionThe resultant mixture is added to the ice water
  10. extractionextracted with ether
  11. extractionThe ether extract
  12. washis washed with saturated aqueous solution of sodium chloride, aqueous solution of sodium hydrogen carbonate and water in order
  13. customthe ether is evaporated
  14. dissolutionThe residue (7.2 g) is dissolved in benzene
  15. custompurified by chromatography on silica gel

Sources & evidence

ORD record
ord-bb4d3a1c07c141d4b4ff8afab60ea60b
Source dataset
uspto-grants-1976_02
Patent number
US03939202

Reaction notes

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