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

HRID 1265278Notes

Reaction equation

HRID 1265278 reaction equation
[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]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 701461-Naphthalenecarbonyl chlorideHCID 5360315Magnesium ChlorideHCID 178461627HCID 178461627, compound

Product 1

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

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

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: 11H 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.

Workup

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

Sources & evidence

ORD record
ord-5b6d08c8b1604296835f4c8655b81b82
Source dataset
uspto-grants-2003_04
Patent number
US06545108B1

Reaction notes

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