tert-Butanol → Ethyl 4-(tert-butoxy)-3-oxobutanoate

HRID 2064670ノート

反応式

HRID 2064670 の反応式
[H-].[Na+].[CH2:3]([O:5][C:6](=[O:12])[CH2:7][C:8]([CH2:10]Cl)=[O:9])[CH3:4].[C:13]([OH:17])([CH3:16])([CH3:15])[CH3:14]>CN(C)C=O>[CH2:3]([O:5][C:6](=[O:12])[CH2:7][C:8](=[O:9])[CH2:10][O:17][C:13]([CH3:16])([CH3:15])[CH3:14])[CH3:4]

参加物

5

反応物 3

HCID 6386tert-ButanolHCID 24758Sodium hydrideHCID 69484Ethyl 4-chloroacetoacetate

生成物 1

HCID 11790264Ethyl 4-(tert-butoxy)-3-oxobutanoate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

A suspension of sodium hydride (4.44 g, 60% dispersion in mineral oil) in dimethyl formamide (50 ml), at 0° C., was treated dropwise with ethyl-4-chloroacetoacetate (5 ml) and then with tert-butyl alcohol (7.08 ml). This mixture was maintained at 0° C. for 2 hours, then a further 2 hours at ambient temperature and then poured onto 2N hydrochloric acid/ice and then extracted four times with ethyl acetate. The combined extracts were washed with saturated aqueous sodium hydrogen carbonate solution, then with water, then with brine, then dried over magnesium sulfate and then evaporated. The resulting yellow oil was subjected to flash column chromatography on silica eluting with a mixture of ethyl acetate and petrol (1:9, v/v) to give 4-tert-butoxy-3-oxo-butyric acid ethyl ester (5.20 g) as a yellow oil. TLC (silica, 1:4, v/v ethyl acetate/petrol): RF=0.51. NMR (400 MHz, CDCl3): δ 1.21 (9H, s), 1.28 (3H, t), 3.55 (2H, s), 4.19 (2H, q).

後処理

  1. extractionextracted four times with ethyl acetate
  2. washThe combined extracts were washed with saturated aqueous sodium hydrogen carbonate solution
  3. dry with materialwith water, then with brine, then dried over magnesium sulfate
  4. customevaporated
  5. additionThe resulting yellow oil was subjected to flash column chromatography on silica eluting with a mixture of ethyl acetate and petrol (1:9, v/v)

出典と根拠

ORDレコード
ord-88bc3bf266054b0098b8b10d1b859262
出典データセット
uspto-grants-2012_10
特許番号
US08288425B2

反応ノート

読み込み中…