Lithium Chloride → Ethyl 2-(2-acetamidopyridin-4-yl)-4-bromothiazole-5-carboxylate

HRID 2402106Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2402106
Br[C:2]1[S:3][C:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:5]([Br:7])[N:6]=1.C[Sn](C)(C)[C:15]1[CH:20]=[CH:19][N:18]=[C:17]([NH:21][C:22](=[O:24])[CH3:23])[CH:16]=1.[Cl-].[Li+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:22]([NH:21][C:17]1[CH:16]=[C:15]([C:2]2[S:3][C:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:5]([Br:7])[N:6]=2)[CH:20]=[CH:19][N:18]=1)(=[O:24])[CH3:23]

Komponenten

7

Edukt 3

HCID 433294Lithium ChlorideHCID 59529632N-(4-(trimethylstannyl)pyridin-2-yl)acetamideHCID 66747450Ethyl 2,4-dibromothiazole-5-carboxylate

Produkt 1

HCID 66747706Ethyl 2-(2-acetamidopyridin-4-yl)-4-bromothiazole-5-carboxylateAusbeute 53 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

A mixture of ethyl 2,4-dibromothiazole-5-carboxylate (0.500 g, 1.59 mmol), N-(4-(trimethylstannyl)pyridin-2-yl)acetamide (0.569 g, 1.90 mmol), tetrakis(triphenylphosphine)palladium(0) (91.7 mg, 0.0794 mmol), copper(I) iodide (90.7 mg, 0.476 mmol), and lithium chloride (202 mg, 4.76 mmol) in dioxane (29.1 mL) was degassed with nitrogen and heated at reflux for 1 hr. The reaction was cooled and concentrated in vacuo. The residue was purified by silica gel chromatography (ethyl acetate/hexane=0/100→50/50) to give 312 mg of the title compound. (44% yield). LC/MS (FA) ES+ 370, 372. 1H NMR (400 MHz, CDCl3) δ: 8.71 (s, 1H), 8.39 (d, 1H, J=5.2 Hz), 8.25 (bs, 1H), 7.68 (dd, 1H, J=5.2, 1.6 Hz), 4.41 (q, 2H, J=7.2 Hz), 2.26 (s, 3H), 1.41 (t, 3H, J=7.2 Hz).

Aufarbeitung

  1. customwas degassed with nitrogen
  2. temperatureheated
  3. temperatureat reflux for 1 hr
  4. temperatureThe reaction was cooled
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel chromatography (ethyl acetate/hexane=0/100→50/50)

Quellen und Nachweise

ORD-Eintrag
ord-efd2d47bec5b4c8faf957a14531124c1
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08796271B2

Notizen zur Reaktion

Wird geladen…