Cesium carbonate → (4-Chloro-3-fluoro-phenyl)-propynoic acid ethyl ester

HRID 527494Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 527494
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[F:9].C(=O)([O-])[O-].[Cs+].[Cs+].[C:16]([O:20][CH2:21][CH3:22])(=[O:19])[C:17]#[CH:18]>O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH2:21]([O:20][C:16](=[O:19])[C:17]#[C:18][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[C:3]([F:9])[CH:4]=1)[CH3:22]

Komponenten

6

Edukt 3

HCID 10796Cesium carbonateHCID 12182Ethyl propiolateHCID 27365631-Chloro-2-fluoro-4-iodobenzene

Produkt 1

HCID 58312631(4-Chloro-3-fluoro-phenyl)-propynoic acid ethyl esterAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
35 °C

Versuchsvorschrift

To a mixture of 4-chloro-3-fluoroiodobenzene (74.27 g, 284 mmol) and cesium carbonate (185.0 g, 568 mmol) in tetrahydrofuran (730 mL) was added under an argon atmosphere cuprous iodide (2.16 g, 11.4 mmol) and bis(triphenylphosphine)palladium (II) chloride (3.98 g, 5.7 mmol). Ethyl propiolate (57.0 g, 575 mmol) was added dropwise over a period of 20 min. The resulting dark brown suspension was stirred for 38 h at 35° C., then filtrated over Hyflo® and the residue was washed with tetrahydrofuran (285 ml). The filtrate was evaporated and purification of the residue by chromatography (SiO2, heptane: ethyl acetate=90:10) afforded the title compound (57.1 g, 89%) as a yellow liquid. MS m/e: 226.0 [M]+.

Aufarbeitung

  1. filtrationfiltrated over Hyflo®
  2. washthe residue was washed with tetrahydrofuran (285 ml)
  3. customThe filtrate was evaporated
  4. custompurification of the residue by chromatography (SiO2, heptane: ethyl acetate=90:10)

Quellen und Nachweise

ORD-Eintrag
ord-7b24701b3b8e481dba7bb864658fb210
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09346786B2

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