Propargyl alcohol → 2-Propynyl 2-(diethoxyphosphoryl)acetate

HRID 1050628Notes

Reaction equation

HRID 1050628 reaction equation
[CH2:1]([O:3][P:4]([CH2:9][C:10](Cl)=[O:11])([O:6][CH2:7][CH3:8])=[O:5])[CH3:2].[CH2:13]([OH:16])[C:14]#[CH:15].C(N(CC)CC)C>C1(C)C=CC=CC=1>[CH2:7]([O:6][P:4]([CH2:9][C:10]([O:16][CH2:13][C:14]#[CH:15])=[O:11])([O:3][CH2:1][CH3:2])=[O:5])[CH3:8]

Participants

5

Reactant 3

HCID 7859Propargyl alcoholHCID 8471TriethylamineHCID 10822542(Diethoxyphosphoryl)acetyl chloride

Product 1

HCID 867092592-Propynyl 2-(diethoxyphosphoryl)acetateYield 93%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
5 °C

Procedure

The above 2-(diethoxyphosphoryl)acetic acid chloride and 31.4 g (0.56 mol) of propargyl alcohol were dissolved in 100 mL of toluene and cooled to 5° C. 67.1 g (0.66 mol) of triethylamine was dropwise added to the solution at 15° C. or lower, then stirred at room temperature for 90 minutes, and disappearance of the starting materials was confirmed through gas chromatography. The formed salt was filtered and washed with 30 ml of a saturated saline solution. The organic layer was concentrated under reduced pressure, and the resulting residue was purified through silica gel column chromatography (ethyl acetate/hexane=1/1 for elution) to give 111.9 g (yield 93%) of the intended 2-propynyl 2-(diethoxyphosphoryl)acetate. The obtained 2-propynyl 2-(diethoxyphosphoryl)acetate was analyzed through 1H-NMR to confirm the structure thereof. The results are shown below.

Workup

  1. filtrationThe formed salt was filtered
  2. washwashed with 30 ml of a saturated saline solution
  3. concentrationThe organic layer was concentrated under reduced pressure
  4. customthe resulting residue was purified through silica gel column chromatography (ethyl acetate/hexane=1/1 for elution)

Sources & evidence

ORD record
ord-d85ab695436742e8ae88aa75d8df8967
Source dataset
uspto-grants-2016_07
Patent number
US09384906B2

Reaction notes

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