Nitromethane → 8-(Nitromethyl)-1,4-dioxaspiro[4.5]decan-8-ol

HRID 1469249

Reaction equation

HRID 1469249 reaction equation
[CH2:1]1[O:11][C:4]2([CH2:9][CH2:8][C:7](=[O:10])[CH2:6][CH2:5]2)[O:3][CH2:2]1.[N+:12]([CH3:15])([O-:14])=[O:13].[O-]CC.[Na+]>C(O)C>[N+:12]([CH2:15][C:7]1([OH:10])[CH2:6][CH2:5][C:4]2([O:3][CH2:2][CH2:1][O:11]2)[CH2:9][CH2:8]1)([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 2723922Sodium ethoxide

Product 1

HCID 468356938-(Nitromethyl)-1,4-dioxaspiro[4.5]decan-8-olYield 40%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

To a solution of 1,4-cyclohexanedione mono-ethylene ketal (30.0 g, 192 mmol) and nitromethane (15.6 mL, 288 mmol) in ethanol (18 mL) was added a solution of sodium ethoxide in ethanol (2.67 M, 3.4 mL, 9.6 mmol). The solution was stirred at room temperature (rt) for 5 days (d), then was concentrated under reduced pressure to a brown oil that was partitioned between water (100 mL) and dichloromethane (100 mL). The aqueous layer was extracted with dichloromethane (3×100 mL). The organic layers were combined, dried over Na2SO4, filtered, and concentrated to a light brown oil. Purification by flash chromatography (silica gel, 40% ethyl acetate/hexanes) provided the product 8-(nitromethyl)-1,4-dioxaspiro[4.5]decan-8-ol as a clear oil (16.7 g, 40%) that slowly formed clear crystals overnight.

Workup

  1. concentrationwas concentrated under reduced pressure to a brown oil that
  2. customwas partitioned between water (100 mL) and dichloromethane (100 mL)
  3. extractionThe aqueous layer was extracted with dichloromethane (3×100 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated to a light brown oil
  7. customPurification by flash chromatography (silica gel, 40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-228220766f304624a064735aa2699191
Source dataset
uspto-grants-2015_04
Patent number
US09006264B2

Linked notes

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