Ethylene Glycol → 1,3-Dioxolane-2,2-diacetic acid, diethyl ester

HRID 595947Notes

Reaction equation

HRID 595947 reaction equation
[CH3:1][CH2:2][O:3][C:4]([CH2:6][C:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:8])=[O:5].[CH2:15](O)[CH2:16][OH:17].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1C=CC=CC=1>[O:8]1[CH2:15][CH2:16][O:17][C:7]1([CH2:6][C:4]([O:3][CH2:2][CH3:1])=[O:5])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11]

Participants

5

Reactant 3

HCID 174Ethylene GlycolHCID 66045Diethyl acetonedicarboxylateHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 2743481,3-Dioxolane-2,2-diacetic acid, diethyl esterYield 42%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of diethyl 1,3-acetonedicarboxylate (12 g, 59.3 mmol), ethyleneglycol (9.93 mL, 178 mmol), and p-toluenesulfonic acid monohydrate (564 mg, 2.97 mmol) in benzene (80 mL) was refluxed under heating removing water for 10 h by Dean-Stark trap. The benzene layer was washed with a saturated aqueous sodium bicarbonate solution and brine. The solvent was distilled away and the residue obtained was purified by flash chromatography (10 to 40% EtOAc in heptanes) yielding diethyl 2,2′-(1,3-dioxolane-2,2-diyl)diacetate (42%). LCMS (m/z): 247.2 (MH+), 0.65 min; 1H NMR (400 MHz, CDCl3) δ ppm 4.17 (q, J=7.04 Hz, 4H) 4.03 (s, 4H) 2.95 (s, 4H) 1.27 (t, J=7.24 Hz, 6H).

Workup

  1. temperatureunder heating
  2. customremoving water for 10 h by Dean-Stark trap
  3. washThe benzene layer was washed with a saturated aqueous sodium bicarbonate solution and brine
  4. distillationThe solvent was distilled away
  5. customthe residue obtained
  6. customwas purified by flash chromatography (10 to 40% EtOAc in heptanes)

Sources & evidence

ORD record
ord-fabe678d23da4b718c5572963ce22991
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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