Triethylamine → Ethyl 2-methylaminoindolizine-3-carboxylate

HRID 502475Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 502475
[Br-].[CH2:2]([O:4][C:5]([CH2:7][N+:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:6])[CH3:3].CSC(SC)=C[N+]([O-])=O.[CH3:23][CH2:24][N:25](CC)[CH2:26]C>C(O)C>[CH3:26][NH:25][C:24]1[CH:23]=[C:13]2[N:8]([C:7]=1[C:5]([O:4][CH2:2][CH3:3])=[O:6])[CH:9]=[CH:10][CH:11]=[CH:12]2

Komponenten

5

Edukt 3

HCID 8471TriethylamineHCID 836231,1-Bis(methylthio)-2-nitroethyleneHCID 87028Pyridinium, 1-(2-ethoxy-2-oxoethyl)-, bromide (1:1)

Produkt 1

HCID 12632503Ethyl 2-methylaminoindolizine-3-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

A mixture of 1-ethoxycarbonylmethylpyridinium bromide 5 (1 g, 4.1 mmol), 1,1-bismethylthio-2-nitroethene (1.2 g; 8.1 mmol) and Et3N (4.1 g, 40.6 mmol) in ethanol (30 mL) was heated at reflux for 12 h. The solvents and the triethylamine were then evaporated under vacuum. The oil obtained was extracted with water (50 mL) and toluene (3×50 mL). The combined extracts were dried over anhydrous magnesium sulphate, filtered and then concentrated under vacuum. The residue was chromatographed on a column of silica with an elution gradient of 1/1 to 4/1 of ethyl acetate/petroleum ether. This gave 0.5 g of ethyl 2-methylaminoindolizine-3-carboxylate 6 in the form of an oil. 1H NMR (DMSO-d6) δ: 9.11 (br s, 1H), 7.32 (d, J=8.8 Hz, 1H), 7.07-7.01 (m, 1H), 6.71-6.66 (m, 1H), 5.88 (br s, 1H), 5.85 (s, 1H), 4.32 (q, J=7.0 Hz, 2H), 2.85 (d, J=5.1 Hz, 3H), 1.34 (t, J=7.0 Hz, 1H), 13C NMR (CDCl3) δ: 161.0, 148.9, 138.2, 127.0, 123.4, 115.8, 109.9, 98.6, 84.3, 58.7, 31.0, 14.7.

Aufarbeitung

  1. temperaturewas heated
  2. temperatureat reflux for 12 h
  3. customThe solvents and the triethylamine were then evaporated under vacuum
  4. customThe oil obtained
  5. extractionwas extracted with water (50 mL) and toluene (3×50 mL)
  6. dry with materialThe combined extracts were dried over anhydrous magnesium sulphate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe residue was chromatographed on a column of silica with an elution gradient of 1/1 to 4/1 of ethyl acetate/petroleum ether

Quellen und Nachweise

ORD-Eintrag
ord-4822f2c394654cc28d0b4a10b6eaffc5
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07776107B2

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