Ethyl orthoformate → Methyl (8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)acetate

HRID 31582

反応式

HRID 31582 の反応式
[O:1]1[CH2:5][CH2:4][O:3][C:2]1([CH2:8][OH:9])[CH2:6][OH:7].[C:10]([CH2:14][C:15]([O:17][CH3:18])=[O:16])(=O)[CH2:11][CH3:12].C(OCC)(OCC)OCC.C(=O)([O-])O.[Na+]>O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(OCC)(=O)C>[CH3:18][O:17][C:15](=[O:16])[CH2:14][C:10]1([CH2:11][CH3:12])[O:9][CH2:8][C:2]2([O:3][CH2:4][CH2:5][O:1]2)[CH2:6][O:7]1

参加物

7

反応物 4

HCID 31214Ethyl orthoformateHCID 121699Methyl 3-oxovalerateHCID 516892Sodium BicarbonateHCID 53755808Dioxolane diyldimethanol

生成物 1

HCID 59792569Methyl (8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)acetate収率 35.8%

試薬・触媒・溶媒 2

HCID 521998p-Toluenesulfonic acid monohydrate触媒HCID 8857Ethyl Acetate溶媒

実験手順

The 1,3-dioxolan-2,2-diyldimethanol (4 g, 29.8 mmol), which was obtained at another time in the same manner as described in the steps (4a)-(4c), was mixed with methyl propionylacetate (5.6 ml, 44.6 mmol) and triethyl orthoformate (5.2 ml, 31.3 mmol), and p-toluenesulfonic acid monohydrate (163 mg, 0.856 mmol). The mixture was stirred at room temperature for 3 hours. To the mixture, a saturated aqueous solution of sodium hydrogen carbonate and ethyl acetate were added. The organic layer was washed with water twice and with an aqueous saline solution, dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by silica gel column chromatography (elution solvent: heptane/ethyl acetate=1/0-3/1-1/1 gradient) and a desired fraction(s) was concentrated to obtain the title compound (2.63 g, yield: 35.8%) as a colorless oil.

後処理

  1. washThe organic layer was washed with water twice
  2. dry with materialwith an aqueous saline solution, dried over anhydrous sodium sulfate
  3. concentrationconcentrated
  4. customThe obtained crude product
  5. customwas purified by silica gel column chromatography (elution solvent: heptane/ethyl acetate=1/0-3/1-1/1 gradient)
  6. concentrationa desired fraction(s) was concentrated

出典と根拠

ORDレコード
ord-17513ed1fa124242b59d9b81904f137b
出典データセット
uspto-grants-2008_09
特許番号
US07425634B2

関連ノート

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