Water → 2-Propargyl-3-hydroxy-3-methyl-4-cyclopentenone

HRID 223784

Reaction equation

HRID 223784 reaction equation
[OH2:1].[CH3:2][C:3]1[O:7][C:6]([CH:8]([CH2:10][C:11]#[CH:12])O)=[CH:5][CH:4]=1.[OH-].[Na+].[Cl-].[Na+]>C([O-])(=O)C.[Na+].C(O)(=O)C>[CH2:10]([CH:8]1[C:3]([OH:7])([CH3:2])[CH:4]=[CH:5][C:6]1=[O:1])[C:11]#[CH:12]

Participants

7

Reactant 4

HCID 962WaterHCID 5234Sodium ChlorideHCID 14798Sodium Hydroxide2×HCID 98774181-(5-Methylfuran-2-yl)but-3-yn-1-ol

Product 1

HCID 130367862-Propargyl-3-hydroxy-3-methyl-4-cyclopentenone

Reagents, catalysts & solvents 2

HCID 517045Sodium AcetateCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
40 °C

Procedure

In a reaction vessel, water (1600 ml), anhydrous sodium acetate (0.4 g) and 5-methyl-2-furylpropargylcarbinol (20 g) were charged, and the temperature was elevated to reflux. The pH value was adjusted to 4.5 with an aqueous 0.5 N acetic acid solution, and the mixture was stirred under reflux for 13 hours while maintaining a pH value of 4.0 to 5.0 by the addition of an aqueous 1/3 N NaOH solution. Then, the reaction mixture was cooled to 40° C., neutralized with an aqueous 1/3 N NaOH solution and, after addition of sodium chloride (300 g), extracted with methyl isobutyl ketone (400 ml) five times. From the extract, methyl isobutyl ketone was removed by distillation at 60° c. under reduced pressure to give an oily substance (16 g), which was subjected to distillation under reduced pressure to obtain 2-propargyl-3-hydroxy-3-methyl-4-cyclopentenone (14.8 g). Yield, 74%. B.P., 115°-132° C./0.1 mmHg. nD25 1.5124. C13NMR spectrum (CDCl3, internal standard TMS, δ ppm, 22.6 MHz): 206.2 (1-C); 167.8 (5-C); 130.7 (4-C); 82.0 (--CH2 -C≡CH); 78.5 (3-C); 70.6 (--CH2 --C≡CH); 57.0 (2-C); 23.4 (--CH3); 14.7 (--CH2 --C≡CH).

Workup

  1. temperatureto reflux
  2. temperatureunder reflux for 13 hours
  3. temperaturewhile maintaining a pH value of 4.0 to 5.0
  4. extractionextracted with methyl isobutyl ketone (400 ml) five times
  5. customFrom the extract, methyl isobutyl ketone was removed by distillation at 60° c
  6. customunder reduced pressure to give an oily substance (16 g), which
  7. distillationwas subjected to distillation under reduced pressure

Sources & evidence

ORD record
ord-e6226aaea418417284b4319816bfead6
Source dataset
uspto-grants-1982_10
Patent number
US04356326

Linked notes

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