Nitromethane → Methyl 2-(8-(nitromethyl)-1,4-dioxaspiro[4.5]decan-8-yl)acetate

HRID 1505690Notes

Reaction equation

HRID 1505690 reaction equation
[O:1]1[C:5]2([CH2:10][CH2:9][C:8](=[CH:11][C:12]([O:14][CH3:15])=[O:13])[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[N+:16]([CH3:19])([O-:18])=[O:17].[F-].C([NH3+])(C)(C)C>C1COCC1.O>[N+:16]([CH2:19][C:8]1([CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH2:7][CH2:6][C:5]2([O:4][CH2:3][CH2:2][O:1]2)[CH2:10][CH2:9]1)([O-:18])=[O:17]

Participants

6

Reactant 3

HCID 6375NitromethaneHCID 11063747Methyl 2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetateHCID 21866379t-Butylammonium fluoride

Product 1

HCID 57795518Methyl 2-(8-(nitromethyl)-1,4-dioxaspiro[4.5]decan-8-yl)acetateYield 49%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of Methyl 1,4-dioxaspiro[4.5]dec-8-ylideneacetate (4 g, 18.8 mmol) in dry THF (20 mL) was treated by nitromethane (1.5 mL, 28.3 mmol) followed by tertbutylammonium fluoride (18.8 mLot a 1M solution in THF, 0.0188 mol). The resulting mixture was stirred at reflux for 18 h under nitrogen. After cooling to RT, the mixture was diluted with water and extracted with MTBE (3×100 mL). Combined organic layers were washed with 10% sodium bicarbonate solution (20 mL), water (100 mL) and brine (50 mL), dried over sodium sulphate filtered and concentrated. Purification by flash chromatography on silica (Pet.Ether:EtOAc) afforded the title compound as a colorless liquid (2.5 g, 49%). 1H NMR (400 MHz, DMSO) δ 4.7 (s, 2H), 3.94 (s, 4H), 3.69 (s, 3H), 2.57 (s, 2H), 1.74 (m, 8H).

Workup

  1. temperatureat reflux for 18 h under nitrogen
  2. extractionextracted with MTBE (3×100 mL)
  3. washCombined organic layers were washed with 10% sodium bicarbonate solution (20 mL), water (100 mL) and brine (50 mL)
  4. dry with materialdried over sodium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by flash chromatography on silica (Pet.Ether:EtOAc)

Sources & evidence

ORD record
ord-1cb1813d784e4a899ce38edf3bbcbfca
Source dataset
uspto-grants-2015_12
Patent number
US09216991B2

Reaction notes

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