تفاعل #498306

معادلة التفاعل

1-naphthoylchloride

Et3N

MgCl2

ethyl potassium malonate

→

3-Naphthalen-1-yl-3-oxo-propionic acid ethyl ester

المردود 66.1%

المذيبات

acetonitrile

ظروف التفاعل

المعالجة

1. 1
   أخرىresulting suspension
2. 2
   workup.STIRRINGstirred under Ar at rt overnight
3. 3
   أخرىThe acetonitrile was removed in vacuo, toluene (14 mL)
4. 4
   workup.ADDITIONwas added
5. 5
   تركيزthe suspension was concentrated again
6. 6
   غسيلwashed with 12% Aq. HCl (14.1 mL)
7. 7
   أخرىThe organic layer was removed
8. 8
   تجفيفdried over Na2SO4
9. 9
   ترشيحfiltered
10. 10
    تركيزconcentrated in vacuo
11. 11
    أخرىThe residue was purified via flash chromatography (SiO2, 10% EtOAc/Heptane)

الإجراء التجريبي

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.

المصدر