Sulfuric Acid → 4,8,12-Trimethyltridec-2-yn-1,4-diol

HRID 745334Notes

Reaction equation

HRID 745334 reaction equation
[OH-].[K+].[CH2:3]([OH:6])[C:4]#[CH:5].[CH3:7][CH:8]([CH2:10][CH2:11][CH2:12][CH:13]([CH2:15][CH2:16][CH2:17][C:18]([CH3:20])=[O:19])[CH3:14])[CH3:9].S(=O)(=O)(O)O>O1CCCC1>[CH3:20][C:18]([OH:19])([CH2:17][CH2:16][CH2:15][CH:13]([CH3:14])[CH2:12][CH2:11][CH2:10][CH:8]([CH3:9])[CH3:7])[C:5]#[C:4][CH2:3][OH:6]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 7859Propargyl alcoholHCID 14797Potassium HydroxideHCID 954956,10-Dimethylundecan-2-one

Product 1

HCID 136503394,8,12-Trimethyltridec-2-yn-1,4-diolYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Into a 2-liter, three-neck, round-bottom flask fitted with a mechanical stirrer, a reflux condenser, and an addition funnel was added 210 g (3.60 mol) of finely powdered potassium hydroxide and 500 ml of anhydrous tetrahydrofuran. The resulting reaction mixture was heated to reflux and then 30.0 g (0.54 mol) of propargyl alcohol was slowly added over a 30 minute period with rapid stirring. The mixture was refluxed for 3 hours before 100 g (0.51 mol) of hexahydropseudoionone in 140 ml of tetrahydrofuran was slowly added over a 2-hour period. After an additional 2 hours at reflux, the reaction was cooled to 0° C. and poured onto 1000 g of ice and 360 g of concentrated sulfuric acid with efficient mixing. The resulting aqueous layer was rinsed with 3×100 ml of ether and the combined organic layers were rinsed with 50 ml of water, 3×50 ml of saturated aqueous sodium bicarbonate, and 50 ml of brine. The resulting ethereal solution was dried with 50 g of magnesium sulfate, and the solvent was removed at aspirator pressure with the aid of a rotary evaporator, leaving 110 g of crude product. Vacuum distillation at 40 μHg and 140° C. afforded 92 g (73%) of pure product, i.e. 4,8,12-trimethyltridec-2-yn-1,4-diol.

Workup

  1. customInto a 2-liter, three-neck, round-bottom flask fitted with a mechanical stirrer, a reflux condenser, and an addition funnel
  2. customThe resulting reaction mixture
  3. temperaturewas heated
  4. temperatureto reflux
  5. additionwas slowly added over a 2-hour period
  6. temperatureAfter an additional 2 hours at reflux
  7. washThe resulting aqueous layer was rinsed with 3×100 ml of ether
  8. washthe combined organic layers were rinsed with 50 ml of water, 3×50 ml of saturated aqueous sodium bicarbonate, and 50 ml of brine
  9. dry with materialThe resulting ethereal solution was dried with 50 g of magnesium sulfate
  10. customthe solvent was removed at aspirator pressure with the aid of a rotary evaporator
  11. customleaving 110 g of crude product
  12. distillationVacuum distillation at 40 μHg and 140° C.

Sources & evidence

ORD record
ord-becb3f9585d4446a8709efec30bfb5bc
Source dataset
uspto-grants-1986_07
Patent number
US04598160

Reaction notes

Loading…