Lithium Chloride → Ethyl 5-[2-(acetylamino)pyridin-4-yl]-4-cyano-3-iodothiophene-2-carboxylate

HRID 2401712Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2401712
[C:1]([C:3]1[C:4]([I:14])=[C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[S:6][C:7]=1I)#[N:2].C[Sn](C)(C)[C:17]1[CH:22]=[CH:21][N:20]=[C:19]([NH:23][C:24](=[O:26])[CH3:25])[CH:18]=1.[Cl-].[Li+]>O1CCOCC1.[Cu]I.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>[C:24]([NH:23][C:19]1[CH:18]=[C:17]([C:7]2[S:6][C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([I:14])[C:3]=2[C:1]#[N:2])[CH:22]=[CH:21][N:20]=1)(=[O:26])[CH3:25]

Komponenten

7

Edukt 3

HCID 433294Lithium ChlorideHCID 59529632N-(4-(trimethylstannyl)pyridin-2-yl)acetamideHCID 66748000Ethyl 4-cyano-3,5-diiodothiophene-2-carboxylate

Produkt 1

HCID 66747307Ethyl 5-[2-(acetylamino)pyridin-4-yl]-4-cyano-3-iodothiophene-2-carboxylateAusbeute 65 %

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

To a solution of ethyl 4-cyano-3,5-diiodothiophene-2-carboxylate (0.473 g, 1.09 mmol) and N-[4-(trimethylstannyl)pyridin-2-yl]acetamide (0.392 g, 1.31 mmol) in dioxane (10.2 mL) was added lithium chloride (0.139 g, 3.28 mmol), copper(I) iodide (0.0624 g, 0.328 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.0947 g, 0.0819 mmol). The reaction flask was evacuated and backfilled with argon, then the solution was heated at 110° C. for 2 hours. The mixture was cooled to room temperature and a mixture of dichloromethane and methanol was added until almost all solids had dissolved. The suspension was filtered through celite and the filtrate was evaporated. Column chromatography was performed to yield the title compound (0.312 g, 65%). LCMS: (FA) ES+ 442. 1H NMR (400 MHz, d6-DMSO) δ: 8.54-8.49 (m, 2H), 8.31 (s, 1H), 4.38-4.32 (m, 2H), 2.13 (s, 3H), 1.36-1.29 (m, 3H).

Aufarbeitung

  1. customThe reaction flask was evacuated
  2. temperatureThe mixture was cooled to room temperature
  3. additiona mixture of dichloromethane and methanol
  4. additionwas added until almost all solids
  5. dissolutionhad dissolved
  6. filtrationThe suspension was filtered through celite
  7. customthe filtrate was evaporated

Quellen und Nachweise

ORD-Eintrag
ord-bdb9c395810e4a3f902df8f77511fc2e
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08796268B2

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