Potassium Carbonate → 3-(5,6,7,8-Tetrahydro-naphthalen-1-yloxy)-but-2-enoic acid ethyl ester

HRID 19059

Reaktionsgleichung

Reaktionsgleichung von HRID 19059
[C:1]1([OH:11])[C:10]2[CH2:9][CH2:8][CH2:7][CH2:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.[CH2:12]([O:14][C:15](=[O:19])[C:16]#[C:17][CH3:18])[CH3:13].C(=O)([O-])[O-].[K+].[K+]>O1CCCC1.CN(C)C1C=CN=CC=1>[CH2:12]([O:14][C:15](=[O:19])[CH:16]=[C:17]([O:11][C:1]1[C:10]2[CH2:9][CH2:8][CH2:7][CH2:6][C:5]=2[CH:4]=[CH:3][CH:2]=1)[CH3:18])[CH3:13]

Komponenten

6

Edukt 3

HCID 11430Potassium CarbonateHCID 682585,6,7,8-Tetrahydro-1-naphtholHCID 78043Ethyl 2-butynoate

Produkt 1

HCID 668949023-(5,6,7,8-Tetrahydro-naphthalen-1-yloxy)-but-2-enoic acid ethyl esterAusbeute 72,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A mixture of 5,6,7,8-tetrahydro-naphthalen-1-ol (3.00 g, 20.24 mmol) and ethyl-2-butynoate (13.62 g, 121.46 mmol) in tetrahydrofuran (100 mL) was treated with potassium carbonate (3.10 g, 22.43 mmol) and 4-dimethylaminopyridine (0.26 g, 2.12 mmol). The reaction was then heated at 85° C. overnight. 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 ethyl acetate (200 mL) and was washed with water (1×100 mL) and a saturated aqueous sodium chloride solution (1×100 mL). The organics were then dried over magnesium sulfate, filtered, rinsed with ethyl acetate and concentrated in vacuo. The material was taken up in ethyl acetate and absorbed onto silica gel. Purification by Analogix flash chromatography (115 g, 1-10% ethyl acetate/hexanes) afforded 3-(5,6,7,8-tetrahydro-naphthalen-1-yloxy)-but-2-enoic acid ethyl ester (3.82 g, 72%) as a light yellow oil: HR-ES-MS m/z calculated for C26H34N4O5 [M+H]+ 483.2602, observed 483.2603; 1H NMR (400 MHz, DMSO-d6) δ ppm 1.11 (t, J=7.1 Hz, 3H), 1.61-1.77 (m, 4H), 2.44 (s, 3H), 2.46 (br. s., 2H), 2.76 (br. s., 2H), 3.98 (q, J=7.1 Hz, 2H), 4.57 (s, 1H), 6.84 (d, J=7.7 Hz, 1H), 7.03 (d, J=7.7 Hz, 1H), 7.18 (t, J=7.7 Hz, 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 ethyl acetate (200 mL)
  4. washwas washed with water (1×100 mL)
  5. dry with materialThe organics were then dried over magnesium sulfate
  6. filtrationfiltered
  7. washrinsed with ethyl acetate
  8. concentrationconcentrated in vacuo
  9. customabsorbed onto silica gel
  10. customPurification by Analogix flash chromatography (115 g, 1-10% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-d0cf0b83a9764c38bc552b256341a71d
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07741327B2

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