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

HRID 1505690Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1505690
[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]

Komponenten

6

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-1cb1813d784e4a899ce38edf3bbcbfca
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09216991B2

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