Sodium hydride → HCID 53830096, compound

HRID 1578812Notes

Reaction equation

HRID 1578812 reaction equation
[H-].[Na+].[CH3:3][CH:4]([CH2:13][CH2:14][CH:15]=[C:16]([CH3:23])[CH2:17][CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])[C:5](=[O:12])[CH2:6][C:7](OCC)=O.Br[CH2:25][C:26](C)=[CH:27][CH2:28][CH2:29][C:30]([CH3:37])=[CH:31][CH2:32][O:33]C(=O)C>CCOCC>[CH3:37][C:30]([CH2:29][CH2:28][CH:27]=[C:26]([CH3:25])[CH2:7][CH2:6][C:5](=[O:12])[CH:4]([CH3:3])[CH2:13][CH2:14][CH:15]=[C:16]([CH3:23])[CH2:17][CH2:18][CH:19]=[C:20]([CH3:21])[CH3:22])=[CH:31][CH2:32][OH:33]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 53963170HCID 53963170, compoundHCID 54451904HCID 54451904, compound

Product 1

HCID 53830096HCID 53830096, compoundYield 96.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

To a suspension of sodium hydride (2.64 g) in ether (70 ml), a solution of ethyl 3,7,11-trimethyl-6,10-dodecadien-2-one-1-carboxylate (14.7 g) in ether (15 ml) is dropwise added, and then a solution of 1-bromo-8-acetoxy-2,6-dimethyl-2,6-octadiene (15 g) in ether (15 ml) is dropwise added thereto while cooling with ice. The reaction mixture is poured into ice water. The ether layer is washed with water, dried and evaporated. The residue (24.8 g) is added to a solution of potassium hydroxide (8.4 g) in ethanol (150 ml), and the resultant mixture is poured into water, followed by washing with petroleum ether, acidifying with 5% aqueous solution of sulfuric acid and extracting with ether. The ether layer is washed with water, dried and evaporated. The resulting product (23.5 g) is purified by chromatography on silica gel (235 g) using benzene to give 3,7,11,15,19-pentamethyl-2,6,14,18-eicosatetraen-10-on-1-ol (18 g). IR: 3400, 1000 cm-1 (OH): 1705 cm-1 (C=O); 1668 cm-1 (C=C). NMR (carbon tetrachloride): δ 1.04 (d), 1.59 (s), 1.66 (s), 2.01 (m), 2.7 (m), 4.1 (m), 5.05 (m).

Workup

  1. temperaturewhile cooling with ice
  2. washThe ether layer is washed with water
  3. customdried
  4. customevaporated
  5. additionThe residue (24.8 g) is added to a solution of potassium hydroxide (8.4 g) in ethanol (150 ml)
  6. additionthe resultant mixture is poured into water
  7. washby washing with petroleum ether
  8. extractionextracting with ether
  9. washThe ether layer is washed with water
  10. customdried
  11. customevaporated
  12. customThe resulting product (23.5 g) is purified by chromatography on silica gel (235 g)

Sources & evidence

ORD record
ord-5ec1d810650d4936bc66d09951eab4f6
Source dataset
uspto-grants-1976_02
Patent number
US03939202

Reaction notes

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