Cesium carbonate → (3,4-Dichloro-phenyl)-propynoic acid ethyl ester

HRID 1799769Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1799769
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[Cl:9].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:16]([O:18][C:19](=[O:22])[C:20]#[CH:21])[CH3:17]>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I.C1COCC1>[CH2:16]([O:18][C:19](=[O:22])[C:20]#[C:21][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[C:3]([Cl:9])[CH:4]=1)[CH3:17]

Komponenten

7

Edukt 3

HCID 10796Cesium carbonateHCID 12182Ethyl propiolate2×HCID 88591Benzene, 1,2-dichloro-4-iodo-

Produkt 1

HCID 67233873(3,4-Dichloro-phenyl)-propynoic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
35 °C

Versuchsvorschrift

Under argon atmosphere, a four neck flask was charged with 1,2-dichloro-4-iodo-benzene (222.8 g, 0.80 mol), bis(triphenylphosphine) palladium(II) chloride (11.2 g, 16.0 mmol, 2 mol %), copper(I) iodide (6.09 g, 32.0 mmol, 4 mol %) and dry THF (2.4 l). At r.t., cesium carbonate (526.6 g, 1.60 mol, 2 eq.) was added over 5 minutes. Afterward, propynoic acid ethyl ester (168.6 ml, 1.60 mol, 2 eq.) was added, and the reaction mixture was stirred overnight at 35° C. An additional portion of propynoic acid ethyl ester (17.0 ml, 0.16 mol, 0.2 eq.) was added, and the reaction was stirred for another 4 h at 35° C. The reaction mixture was evaporated to dryness, and the residue was taken up in toluene (0.8 l) and heptane (1.6 l). The resulting suspension was stirred at 40° C. for 1 h and filtered over celite. The filtrate was concentrated, and the product was purified by silica gel filtration (toluene/heptane 1:2) to yield 175.0 g (89%) of Vb as a white solid.

Aufarbeitung

  1. stirringthe reaction was stirred for another 4 h at 35° C
  2. customThe reaction mixture was evaporated to dryness
  3. stirringThe resulting suspension was stirred at 40° C. for 1 h
  4. filtrationfiltered over celite
  5. concentrationThe filtrate was concentrated
  6. filtrationthe product was purified by silica gel filtration (toluene/heptane 1:2)
  7. customto yield 175.0 g (89%) of Vb as a white solid

Quellen und Nachweise

ORD-Eintrag
ord-4f6898244fdc46408571cbb2e0fcc94b
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08344161B2

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