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

HRID 1505690ノート

反応式

HRID 1505690 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-1cb1813d784e4a899ce38edf3bbcbfca
出典データセット
uspto-grants-2015_12
特許番号
US09216991B2

反応ノート

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