Ethyl oxoacetate → (6Z,9Z,29Z,32Z)-19-((9Z,12Z)-octadeca-9,12-dienyl)octatriaconta-6,9,29,32-tetraene-19,20-diol

HRID 1259002Notes

Reaction equation

HRID 1259002 reaction equation
[Mg].[CH2:2](Br)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19].[C:21]([O:25]CC)(=O)[CH:22]=[O:23]>C1COCC1>[CH2:2]([C:22]([OH:23])([CH:21]([OH:25])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

5

Reactant 3

HCID 70211Ethyl oxoacetateHCID 5462224MagnesiumHCID 10065142(6Z,9Z)-18-bromooctadeca-6,9-diene

Product 1

HCID 86667529(6Z,9Z,29Z,32Z)-19-((9Z,12Z)-octadeca-9,12-dienyl)octatriaconta-6,9,29,32-tetraene-19,20-diolYield 48.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 100 mL round bottom flask was charged with magnesium turnings (360 mg, 14.6 mmol) and a stir bar. The flask was dried with a heat gun for 5 minutes then cooled under nitrogen. The flask was charged with THF (5 mL) and a small grain of iodine. A solution of linoleyl bromide (4 g, 12.1 mmol) in THF (5 mL) was added slowly and after 5 minutes the reaction initiated vigorously. The solution was stirred at room temperature for 2 hours, and then ethyl glyoxalate (0.5 mL, 2.42 mmol, 50% solution in toluene) was added. The exothermic reaction was finished immediately and quenched with saturated ammonium chloride solution (5 mL). The solution diluted with water and extracted with diethyl ether (3×50 mL). The combined diethyl ether extracts were dried on magnesium sulfate, filtered and concentrated in vacuo to dryness. The oil was purified by column chromatography on silica gel 60 (eluted with 100% Hexanes to 15% Et2O in hexanes) to afford (6Z,9Z,29Z,32Z)-19-((9Z,12Z)-octadeca-9,12-dienyl)octatriaconta-6,9,29,32-tetraene-19,20-diol as a colorless oil (945 mg, 48%).

Workup

  1. customThe flask was dried with a heat gun for 5 minutes
  2. temperaturethen cooled under nitrogen
  3. additionThe flask was charged with THF (5 mL)
  4. customThe exothermic reaction
  5. customquenched with saturated ammonium chloride solution (5 mL)
  6. additionThe solution diluted with water
  7. extractionextracted with diethyl ether (3×50 mL)
  8. dry with materialThe combined diethyl ether extracts were dried on magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo to dryness
  11. customThe oil was purified by column chromatography on silica gel 60 (eluted with 100% Hexanes to 15% Et2O in hexanes)

Sources & evidence

ORD record
ord-7bc43bbb964a4d25a4863e32ea3fda71
Source dataset
uspto-grants-2013_06
Patent number
US08466122B2

Reaction notes

Loading…