Ethyl orthoformate → Methyl (8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)acetate

HRID 31582

Reaction equation

HRID 31582 reaction equation
[O:1]1[CH2:5][CH2:4][O:3][C:2]1([CH2:8][OH:9])[CH2:6][OH:7].[C:10]([CH2:14][C:15]([O:17][CH3:18])=[O:16])(=O)[CH2:11][CH3:12].C(OCC)(OCC)OCC.C(=O)([O-])O.[Na+]>O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(OCC)(=O)C>[CH3:18][O:17][C:15](=[O:16])[CH2:14][C:10]1([CH2:11][CH3:12])[O:9][CH2:8][C:2]2([O:3][CH2:4][CH2:5][O:1]2)[CH2:6][O:7]1

Participants

7

Reactant 4

HCID 31214Ethyl orthoformateHCID 121699Methyl 3-oxovalerateHCID 516892Sodium BicarbonateHCID 53755808Dioxolane diyldimethanol

Product 1

HCID 59792569Methyl (8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)acetateYield 35.8%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 8857Ethyl AcetateSolvent

Procedure

The 1,3-dioxolan-2,2-diyldimethanol (4 g, 29.8 mmol), which was obtained at another time in the same manner as described in the steps (4a)-(4c), was mixed with methyl propionylacetate (5.6 ml, 44.6 mmol) and triethyl orthoformate (5.2 ml, 31.3 mmol), and p-toluenesulfonic acid monohydrate (163 mg, 0.856 mmol). The mixture was stirred at room temperature for 3 hours. To the mixture, a saturated aqueous solution of sodium hydrogen carbonate and ethyl acetate were added. The organic layer was washed with water twice and with an aqueous saline solution, dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by silica gel column chromatography (elution solvent: heptane/ethyl acetate=1/0-3/1-1/1 gradient) and a desired fraction(s) was concentrated to obtain the title compound (2.63 g, yield: 35.8%) as a colorless oil.

Workup

  1. washThe organic layer was washed with water twice
  2. dry with materialwith an aqueous saline solution, dried over anhydrous sodium sulfate
  3. concentrationconcentrated
  4. customThe obtained crude product
  5. customwas purified by silica gel column chromatography (elution solvent: heptane/ethyl acetate=1/0-3/1-1/1 gradient)
  6. concentrationa desired fraction(s) was concentrated

Sources & evidence

ORD record
ord-17513ed1fa124242b59d9b81904f137b
Source dataset
uspto-grants-2008_09
Patent number
US07425634B2

Linked notes

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