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

HRID 1913225Notes

Reaction equation

HRID 1913225 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) were charged to a 1000 mL round-bottom flask. To this flask was added benzene (300 mL) followed by ethylene glycol (0.37 mol, 20.5 mL). The resulting bi-layer solution was refluxed overnight using a Dean-Stark trap. Upon cooling, the reaction mixture was diluted in 300 mL DCM and washed with 300 mL saturated NaHCO3(aq). DCM was used to extract from the aqueous layer (x3) and the combined organics were dried over Na2SO4. The residue was taken up in DCM and purified by silica gel chromatography using a 0% to 50% ethyl acetate in hexanes gradient. The product was monitored via PMA stain. Chromatography yielded 17.05 grams (79.58 mmol, 65% yield) ethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate (Int-5a).

Workup

  1. temperatureThe resulting bi-layer solution was refluxed overnight
  2. temperatureUpon cooling
  3. washwashed with 300 mL saturated NaHCO3(aq)
  4. extractionto extract from the aqueous layer (x3)
  5. dry with materialthe combined organics were dried over Na2SO4
  6. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-5941876df6d74541ba5a3adfb02ce63d
Source dataset
uspto-grants-2013_12
Patent number
US08609675B2

Reaction notes

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