Methanol → Acetic acid, 2-(1,4-dioxaspiro(4.5)dec-8-ylidene)-, ethyl ester

HRID 2353820Notes

Reaction equation

HRID 2353820 reaction equation
[CH2:1]1[CH2:5][O:4][CH2:3][CH2:2]1.[H-].[Li+].[O:8]1[C:12]2([CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]2)[O:11][CH2:10][CH2:9]1.C[OH:20]>O>[O:8]1[C:12]2([CH2:17][CH2:16][C:15](=[CH:2][C:3]([O:4][CH2:5][CH3:1])=[O:20])[CH2:14][CH2:13]2)[O:11][CH2:10][CH2:9]1

Participants

6

Reactant 4

HCID 887MethanolHCID 8028TetrahydrofuranHCID 62714Lithium hydrideHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 373318Acetic acid, 2-(1,4-dioxaspiro(4.5)dec-8-ylidene)-, ethyl esterYield 93%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of THF (18 mL) under argon was added 0.38 g (47.8 mmol, 5 equiv) of LiH, followed by slow addition of 8.78 g (47.8 mmol, 5 equiv) of triethyl phosphonoacetate. The solution was stirred at rt for 1 h and 1.49 g (9.6 mmol, 1 equiv) of 1,4-dioxa-spiro[4.5]decan-8-one was added and the solution was heated at 65° C. for 16 h. Upon cooling the solution was treated with MeOH (10 mL) and water (5 mL) and concentrated in vacuo. The resulting yellow oil was purified by silica gel chromatography eluting with 4:1 Hex/EtOAc to yield 1.89 g (93%) of a clear oil. 1H-NMR (CDCl3-d) δ 5.67 (s, 1H), 4.16 (t, 2H), 3.99 (m, 4H), 3.02 (m, 2H), 2.39 (m, 2H), 1.78 (m, 4H), 1.29 (t, 3H); LCMS RT=2.56 min, [M+H]+=226.9.

Workup

  1. temperaturethe solution was heated at 65° C. for 16 h
  2. temperatureUpon cooling the solution
  3. concentrationconcentrated in vacuo
  4. customThe resulting yellow oil was purified by silica gel chromatography
  5. washeluting with 4:1 Hex/EtOAc

Sources & evidence

ORD record
ord-65650c985cd34b12b1770f0b5a98c42b
Source dataset
uspto-grants-2010_07
Patent number
US07750017B2

Reaction notes

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