Methanol → Methyl 7-chlorothieno[3,2-B]pyridine-2-carboxylate

HRID 525794Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 525794
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[CH:9][S:10][C:3]=12.C([Li])CCC.Cl[C:17]([O:19][CH3:20])=[O:18].CO>C1COCC1.ClCCl.CCCCCC.C(OCC)C>[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([C:17]([O:19][CH3:20])=[O:18])[S:10][C:3]=12

Komponenten

8

Edukt 4

HCID 887MethanolHCID 6586Methyl chloroformateHCID 112752517-Chlorothieno[3,2-b]pyridineHCID 178418339Butyllithium

Produkt 1

HCID 59424429Methyl 7-chlorothieno[3,2-B]pyridine-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 21584099Diethylether hexaneLösungsmittel

Versuchsvorschrift

7-chlorothieno[3,2-b]pyridine (19.7 g, 0.116 mol) was taken up in THF (400 mL) and cooled to approximately −70 C. The n-butyllithium (1.6M, 80 mL, 0.128 mol) was added dropwise with stirring under an atmosphere of nitrogen. The solution was stirred at −70 C for 1 hour at which time neat methyl chloroformate was added via dropwise addition. The reaction mixture gradually warmed to room temperature and was stirred for over the weekend. The reaction mixture was treated with 25 mL of methanol and then concentrated to dryness leaving a maroon residue. The crude solid was taken up in dichloromethane and passed through a silica gel column eluting with 1:1 hexane/ethyl acetate. Fractions containing the product were combined and concentrated to give a red solid. Trituration with 9:1 hexane/diethyl ether afforded methyl 7-chlorothieno[3,2-b]pyridine-2-carboxylate as a pink solid after filtration. Yield: 14.5 g (55%); MS [M+H]+ 227.9; 1HNMR (CDCl3) δ: 8.7 (d, 1H), 8.3 (s, 1H), 7.4 (d, 1H) ppm.

Aufarbeitung

  1. temperaturecooled to approximately −70 C
  2. additionwas added via dropwise addition
  3. stirringwas stirred for over the weekend
  4. concentrationconcentrated to dryness
  5. customleaving a maroon residue
  6. washeluting with 1:1 hexane/ethyl acetate
  7. additionFractions containing the product
  8. concentrationconcentrated
  9. customto give a red solid

Quellen und Nachweise

ORD-Eintrag
ord-490aefdf1bd7416cb353719fc94ba182
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09340555B2

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