Methyl iodide → Ethyl 8-methyl-1,4-dioxaspiro[4.5]decane-8-carboxylate

HRID 1913267Notes

Reaction equation

[O:1]1[C:5]2([CH2:10][CH2:9][CH:8]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[Li+].[CH3:17]C([N-]C(C)C)C.CI.[NH4+].[Cl-]>C1COCC1>[CH3:17][C:8]1([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:9][CH2:10][C:5]2([O:4][CH2:3][CH2:2][O:1]2)[CH2:6][CH2:7]1

Participants

Conditions

Temperature: -78 °C

Procedure

Ethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate (Int-18a, 2.14 g, 10 mmol) was dissolved in dry THF (20 mL) and the solution was cooled to −78° C. LDA (1.8 M in THF, 6.6 mL) was added to the mixture dropwise and the mixture was stirred for 15 min. Then CH3I (1.87 mL, 30 mmol) was added to the mixture at −78° C. and the reaction was allowed to warm up to room temperature. The reaction was stirred overnight. NH4Cl (aq.) was added to quench the reaction which was extracted with ethyl acetate (50 mL×3). The combined organics was washed with water and brine and dried over Na2SO4. After concentration, the residue was purified by column chromatography (0-50% ethyl acetate in hexane) which gave ethyl 8-methyl-1,4-dioxaspiro[4.5]decane-8-carboxylate (Int-18b) (2.09 g) as an oil. HPLC-MS tR=1.68 min (UV254 nm); mass calculated for formula C12H20O4 228.1, observed LCMS m/z 229.1 (M+H).

Workup

temperatureto warm up to room temperature
stirringThe reaction was stirred overnight
customto quench
customthe reaction which
extractionwas extracted with ethyl acetate (50 mL×3)
washThe combined organics was washed with water and brine
dry with materialdried over Na2SO4
concentrationAfter concentration
customthe residue was purified by column chromatography (0-50% ethyl acetate in hexane) which

Sources & evidence

ORD record: ord-a455606ced6048c69c86a374f283b015
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08609675B2

Reaction notes

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