Triethylamine → Ethyl 3-(naphthalen-8-yl)-3-oxopropanoate

HRID 411124

反応式

HRID 411124 の反応式
[C:1]([OH:7])(=[O:6])[CH2:2][C:3]([OH:5])=O.[CH2:8]([K])[CH3:9].CCN(CC)CC.[Mg+2].[Cl-].[Cl-].[C:21]1(C(Cl)=O)[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH:24]=[CH:23][CH:22]=1>C(#N)C>[CH2:8]([O:7][C:1](=[O:6])[CH2:2][C:3]([C:29]1[C:30]2[C:25](=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:26]=[CH:27][CH:28]=1)=[O:5])[CH3:9]

参加物

6

反応物 4

HCID 8471TriethylamineHCID 701461-Naphthalenecarbonyl chlorideHCID 5360315Magnesium ChlorideHCID 178461627HCID 178461627、化合物

生成物 1

HCID 2760157Ethyl 3-(naphthalen-8-yl)-3-oxopropanoate収率 66.1%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

A suspension of ethyl potassium malonate (3.4 g, 20.0 mmol) in acetonitrile (30.6 mL) was treated with Et3N (3.11 mL, 22.3 mmol) and MgCl2 (2.38 g, 25.0 mmol). The. resulting suspension was stirred at rt for 2.5 h, then treated with 1-naphthoylchloride (1.55 mL, 10.3 mmol) and stirred under Ar at rt overnight. The acetonitrile was removed in vacuo, toluene (14 mL) was added and the suspension was concentrated again. The residue was suspended in toluene (14 mL) and washed with 12% Aq. HCl (14.1 mL). The organic layer was removed, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified via flash chromatography (SiO2, 10% EtOAc/Heptane) to afford 3-Naphthalen-1-yl-3-oxo-propionic acid ethyl ester (1.65 g, 66%) as a 3.5:1 mixture of keto/enol isomers: 1 1H NMR (CDCl3, chemical shifts in ppm relative to TMS): 1.21 (t, 3H, ketone isomer, J=7.1 Hz), 1.36 (3 h, enol isomer,.J =7.1 Hz), 4.11 (s, 2H, ketone isomer), 4.20 (q, 2H, ketone isomer, J=7.4 Hz), 4.32 (q, 2H, enol isomer, J=7.4 Hz), 5.50 (s, 1H, enol isomer), 7.46-7.68 (m, 3H), 7.88 (d, 1H, J=8.1 Hz), 7.92 (d, 1H, J=7.3 Hz), 8.03 (d, 1H, J=8.1 Hz), 8.36 (d, 1H, enol isomer, J=8.1 Hz), 8.76 (d, 1H, J=8.1 Hz); Field Desorption Mass Spectrometry: m/z 242.

後処理

  1. customresulting suspension
  2. stirringstirred under Ar at rt overnight
  3. customThe acetonitrile was removed in vacuo, toluene (14 mL)
  4. additionwas added
  5. concentrationthe suspension was concentrated again
  6. washwashed with 12% Aq. HCl (14.1 mL)
  7. customThe organic layer was removed
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified via flash chromatography (SiO2, 10% EtOAc/Heptane)

出典と根拠

ORDレコード
ord-18f49641fe5c4ba39fa041457f9bf8d5
出典データセット
uspto-grants-2003_05
特許番号
US06559091B1

関連ノート

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