Diisopropylethylamine → 2-Chloro-5-((2-chlorophenyl)ethynyl)isonicotinaldehyde

HRID 468849Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 468849
Br[C:2]1[C:7]([CH:8]=[O:9])=[CH:6][C:5]([Cl:10])=[N:4][CH:3]=1.[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]#[CH:19].C(N(CC)C(C)C)(C)C>O1CCOCC1.C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:10][C:5]1[CH:6]=[C:7]([C:2]([C:19]#[C:18][C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2[Cl:11])=[CH:3][N:4]=1)[CH:8]=[O:9]

Komponenten

8

Edukt 3

HCID 81531DiisopropylethylamineHCID 5859951-Chloro-2-ethynylbenzeneHCID 534183815-Bromo-2-chloropyridine-4-carbaldehyde

Produkt 1

HCID 866749492-Chloro-5-((2-chlorophenyl)ethynyl)isonicotinaldehydeAusbeute 88,5 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A mixture of 5-bromo-2-chloroisonicotinaldehyde (1.0 g, 4.5 mmol), 1-chloro-2-ethynylbenzene (650 mg, 4.7 mmol), N,N-diisopropylethylamine (1.6 mL, 9.1 mmol), copper(I) iodide (43 mg, 0.23 mmol), and bis(triphenylphosphine)palladium(II) chloride (159 mg, 0.23 mmol) in 1,4-dioxane (21 mL) was heated at 50° C. for 1 hour. The cooled reaction mixture was diluted with ethyl acetate (100 mL) and washed with water (100 mL). The organic layer was separated, dried over sodium sulfate, filtered, and evaporated in vacuo to afford a residue that was purified by flash chromatography (silica, 40 g, ISCO, 0-30% ethyl acetate in heptane) to afford the title compound as an off-white solid (1.1 g, 88%). 1H NMR (400 MHz, CDCl3) δ 10.64 (s, 1H), 8.77 (s, 1H), 7.77 (s, 1H), 7.62 (dd, J=7.5, 1.7 Hz, 1H), 7.49 (d, J=7.9 Hz, 1H), 7.38 (td, J=7.8, 1.8 Hz, 1H), 7.32 (td, J=7.5, 1.2 Hz, 1H).

Aufarbeitung

  1. customThe cooled reaction mixture
  2. washwashed with water (100 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto afford a residue that
  8. customwas purified by flash chromatography (silica, 40 g, ISCO, 0-30% ethyl acetate in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-eca51bf2c1d54d6a888d420eb2f326c1
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08623889B2

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