Diethylene Glycol → HCID 68468916, compound

HRID 888318Notes

Reaction equation

HRID 888318 reaction equation
[CH2:1]([OH:7])[CH2:2][O:3][CH2:4][CH2:5][OH:6].[OH-].[Na+].[CH2:10]([C:12]1([CH2:16]OS(C)(=O)=O)[CH2:15][O:14][CH2:13]1)[CH3:11]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C1(C)C=CC=CC=1>[CH2:10]([C:12]1([CH2:16][O:7][CH2:1][CH2:2][O:3][CH2:4][CH2:5][OH:6])[CH2:15][O:14][CH2:13]1)[CH3:11]

Participants

7

Reactant 3

HCID 8117Diethylene GlycolHCID 14798Sodium HydroxideHCID 16070660HCID 16070660, compound

Product 1

HCID 68468916HCID 68468916, compound

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

Diethylene glycol (500 g (4.7 mol)), tetrabutylammonium bromide (5.0 g (15.5 mmol)) and 96% sodium hydroxide (50 g (1.2 mol)) were added to a glass flask having an inner volume of 1,000 ml equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the mixture was warmed to 70° C. with stirring. Subsequently 3-ethyl-3-methanesulfonyloxymethyloxetane (216 g (1.0 mol)) having a purity of 90% (a value measured by 1H-NMR) was dropwise added and reacted for 2 hours while keeping the liquid temperature at 80-90° C. After the completion of the reaction, water (200 ml) was added to reaction liquid (a bisoxetane ether compound generated in the amount of only 9% (an analysis value by a gas chromatography)), and a liquid separation was performed to give an organic layer. Toluene (200 ml) and water (100 ml) were added to the resultant organic layer, and a liquid separation was performed. Subsequently a resultant aqueous layer was extracted with toluene (100 ml) twice. An extract (a toluene layer) and the previously obtained organic layer were mixed, and the mixture was concentrated under reduced pressure. A resultant concentrate was distilled under reduced pressure (142-145° C., 400 Pa) to give, as a colorless liquid, 3-ethyl-3-(2-hydroxyethyloxyethyl)oxymethyloxetane having a purity of 93% (an analysis value by a gas chromatography) (158 g) (an isolated yield based on 3-ethyl-3-methanesulfonyloxymethyloxetane: 72%).

Workup

  1. customequipped with a stirrer
  2. additionwas dropwise added
  3. customreacted for 2 hours
  4. customat 80-90° C
  5. customa liquid separation
  6. customto give an organic layer
  7. customa liquid separation
  8. extractionSubsequently a resultant aqueous layer was extracted with toluene (100 ml) twice
  9. extractionAn extract (a toluene layer) and the previously obtained organic layer
  10. additionwere mixed
  11. concentrationthe mixture was concentrated under reduced pressure
  12. concentrationA resultant concentrate
  13. distillationwas distilled under reduced pressure (142-145° C., 400 Pa)

Sources & evidence

ORD record
ord-95ad6a6663b744bc8f2f2a24214a7b10
Source dataset
uspto-grants-2012_08
Patent number
US08247583B2

Reaction notes

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