Ethylene Glycol → Ethyl 1,4-dioxaspiro(4.5)decane-8-carboxylate

HRID 2047052Notes

Reaction equation

HRID 2047052 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C1C=CC=CC=1.[CH2:31](O)[CH2:32][OH:33]>C(Cl)Cl>[O:33]1[C:2]2([CH2:7][CH2:6][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]2)[O:1][CH2:31][CH2:32]1

Participants

6

Reactant 4

HCID 174Ethylene GlycolHCID 241BenzeneHCID 317638Ethyl 4-oxocyclohexanecarboxylateHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 10488810Ethyl 1,4-dioxaspiro(4.5)decane-8-carboxylateYield 65%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Ethyl 4-oxocyclohexane carboxylate (122.56 mmol, 20.86 g) and para-toluenesulfonic acid monohydrate (12.56 mmol, 2.33 g) are charged to a 1000 mL roundbottom flask. To this flask was added benzene (300 mL) followed by ethylene glycol (0.37 mol, 20.5 mL). The resulting bi-layer reaction mixture was refluxed overnight in a Dean-Stark trap. Upon cooling, the reaction mixture was diluted in 300 mL DCM and washed with 300 mL saturated NaHCO3(aq). The aqueous layer was washed with DCM (3×) and the combined organics are dried over Na2SO4. The residue was dissolved in DCM and purified by silica gel chromatography on 0% to 50% ethyl acetate in hexanes gradient. The product is tracked via PMA stain. Chromatography yields 17.05 grams (79.58 mmol, 65% yield) ethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate.

Workup

  1. customThe resulting bi-layer reaction mixture
  2. temperaturewas refluxed overnight in a Dean-Stark trap
  3. temperatureUpon cooling
  4. washwashed with 300 mL saturated NaHCO3(aq)
  5. washThe aqueous layer was washed with DCM (3×)
  6. dry with materialthe combined organics are dried over Na2SO4
  7. dissolutionThe residue was dissolved in DCM
  8. custompurified by silica gel chromatography on 0% to 50% ethyl acetate in hexanes gradient

Sources & evidence

ORD record
ord-57011624308942cb96dd36dd83ba0419
Source dataset
uspto-grants-2013_11
Patent number
US08591943B2

Reaction notes

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