1-Naphthol → 3-(Naphthalen-1-yloxy)-but-2-enoic acid ethyl ester

HRID 19072

Reaktionsgleichung

Reaktionsgleichung von HRID 19072
[C:1]1([OH:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[CH2:12]([O:14][C:15](=[O:19])[C:16]#[C:17][CH3:18])[CH3:13].N12CCCN=C1CCCCC2>O1CCCC1>[CH2:12]([O:14][C:15](=[O:19])[CH:16]=[C:17]([O:11][C:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1)[CH3:18])[CH3:13]

Komponenten

5

Edukt 3

HCID 70051-NaphtholHCID 78043Ethyl 2-butynoateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

Produkt 1

HCID 668945063-(Naphthalen-1-yloxy)-but-2-enoic acid ethyl esterAusbeute 50,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

A mixture of naphthalen-1-ol (1.28 g, 8.91 mmol) and ethyl-2-butynoate (2.0 g, 17.8 mmol) in tetrahydrofuran (13.7 mL) was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (1.33 mL, 8.91 mmol). The reaction was then heated at 130° C. for 1.5 h. At this time, the reaction was cooled to 25° C. and was stirred at 25° C. overnight. At this time, the reaction was concentrated in vacuo. The residue was dissolved in dichloromethane (40 mL) and was washed with a 2N aqueous hydrochloric acid solution (1×100 mL), a 0.5N aqueous sodium hydroxide solution (1×100 mL) and a saturated aqueous sodium chloride solution (1×100 mL). The organics were then dried over sodium sulfate, filtered, rinsed with dichloromethane and concentrated in vacuo. Purification by Analogix flash chromatography (40 g, 5-10% ethyl acetate/hexanes) afforded 3-(naphthalen-1-yloxy)-but-2-enoic acid ethyl ester (1.16 g, 50%) as a clear oil: HR-ES-MS m/z calculated for C16H16O3 [M+H]+ 257.1172, observed 257.1172; 1H NMR (300 MHz, DMSO-d6), δ ppm 1.04 (t, J=7.1 Hz, 3H), 2.60 (s, 3H), 3.93 (q, J=7.1 Hz, 2H), 4.52 (s, 1H), 7.31 (d, J=7.2 Hz, 1H), 7.53-7.65 (m, 3H), 7.78-7.84 (m, 1H), 7.90 (d, J=8.2 Hz, 1H), 7.99-8.07 (m, 1H).

Aufarbeitung

  1. temperatureAt this time, the reaction was cooled to 25° C.
  2. concentrationAt this time, the reaction was concentrated in vacuo
  3. dissolutionThe residue was dissolved in dichloromethane (40 mL)
  4. washwas washed with a 2N aqueous hydrochloric acid solution (1×100 mL)
  5. dry with materialThe organics were then dried over sodium sulfate
  6. filtrationfiltered
  7. washrinsed with dichloromethane
  8. concentrationconcentrated in vacuo
  9. customPurification by Analogix flash chromatography (40 g, 5-10% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-9ffb306c33254dcc935c8fd11a656986
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07741327B2

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