Sodium Hydroxide → 1,4-Dioxaspiro[4.5]decan-8-ylmethanol

HRID 1093106Notes

Reaction equation

HRID 1093106 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[O:7]1[C:11]2([CH2:16][CH2:15][CH:14]([C:17](OCC)=[O:18])[CH2:13][CH2:12]2)[O:10][CH2:9][CH2:8]1.[OH-].[Na+]>C1COCC1>[O:7]1[C:11]2([CH2:16][CH2:15][CH:14]([CH2:17][OH:18])[CH2:13][CH2:12]2)[O:10][CH2:9][CH2:8]1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 10488810Ethyl 1,4-dioxaspiro(4.5)decane-8-carboxylateHCID 21226445Aluminium lithium hydride

Product 1

HCID 100808381,4-Dioxaspiro[4.5]decan-8-ylmethanolYield 103.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The procedure of Pearson at al., J. Org. Chem., 1997, 62, 5284 was followed. To a stirred 1M solution of lithium aluminum hydride (148 mL, 148 mmol) cooled to 0° C., in an ice-bath, was added a solution of ethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate (31.8 g, 148 mmol) in THF (30 mL), dropwise, over a period of 50 min. The ice-bath was removed and the mixture stirred under N2 overnight. It was then cooled and water (20 mL) slowly added under vigorous stirring [note: very vigorous reaction with heat and foam generation] followed by the addition of 15% NaOH (20 mL). The insoluble material was removed by filtration through CELITE®, washing with THF. The combined filtrate and washings were dried (Na2SO4), filtered and concentrated to provide the title compound, 1,4-dioxaspiro[4.5]decan-8-ylmethanol (26.3 g, 153 mmol, 103% yield) as a clear oil: LCMS: m/z 173 (M+H) at 0.67 min; 1H NMR (500 MHz, CDCl3) δ ppm 1.11-1.25 (2H, m), 1.39-1.52 (3H, m), 1.70 (4H, d, J=9.5 Hz), 2.75 (1H, s), 3.39 (2H, d, J=6.4 Hz), 3.86-3.89 (4H, m); 13C NMR (126 MHz, CDCl3) δ ppm 26.7, 34.2, 39.1, 64.3, 67.5, 109.2.

Workup

  1. customThe ice-bath was removed
  2. temperatureIt was then cooled
  3. additionwater (20 mL) slowly added
  4. stirringunder vigorous stirring [note
  5. customvery vigorous reaction
  6. temperaturewith heat
  7. customThe insoluble material was removed by filtration through CELITE®
  8. washwashing with THF
  9. dry with materialThe combined filtrate and washings were dried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-bacd2ef76f654533965839b2ea452070
Source dataset
uspto-grants-2012_03
Patent number
US08129398B2

Reaction notes

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