Hydrochloric Acid → Ethyl [(prop-2-yn-1-yl)oxy]acetate

HRID 595093Notes

Reaction equation

HRID 595093 reaction equation
[CH2:1]([OH:4])[C:2]#[CH:3].[H-].[Na+].[CH2:7]([O:9][C:10](=[O:13])[CH2:11]Br)[CH3:8].Cl>C1COCC1>[CH2:7]([O:9][C:10](=[O:13])[CH2:11][O:4][CH2:1][C:2]#[CH:3])[CH3:8]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7748Ethyl bromoacetateHCID 7859Propargyl alcoholHCID 24758Sodium hydride

Product 1

HCID 12883734Ethyl [(prop-2-yn-1-yl)oxy]acetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of prop-2-yn-1-ol (815 g, 14.5 mol) in THF (1 L) is added dropwise to a suspension of NaH (60% content) (500 g) in THF (4 L) at 0° C. under nitrogen atmosphere. The stirring is continued at this temperature for 3 h before a solution of bromo-acetic acid ethylester (2.17 kg, 13.0 mol) in THF (2 L) is added dropwise over 1 h. After addition, the temperature is allowed to warm to RT and the reaction mixture is stirred for another 3 h. HCl (2 M, 8 L) is added into the reaction mixture, the organic layer is isolated and the aqueous layer is extracted with EtOAc (3×5 L). The combined organic layer is washed with brine (2 L), dried over anhydrous Na2SO4 and concentrated in vacuo. The crude oil is distilled to give the desired product. Yield: 1.6 kg. 1H NMR: (CDCl3) δ 4.31 (s, 2H), 4.23 (q, J=7.2 Hz, 2H), 4.19 (s, 2H), 2.47 (t, J=2.4 Hz, 1H), 1.29 (t, J=7.2 Hz, 3H).

Workup

  1. additionis added dropwise over 1 h
  2. additionAfter addition
  3. customthe organic layer is isolated
  4. extractionthe aqueous layer is extracted with EtOAc (3×5 L)
  5. washThe combined organic layer is washed with brine (2 L)
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated in vacuo
  8. distillationThe crude oil is distilled

Sources & evidence

ORD record
ord-fdf04bdabe7145f6ad80595acc94a422
Source dataset
uspto-grants-2016_01
Patent number
US09243000B2

Reaction notes

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