Triethylamine → Methyl 2-(methoxymethylene)-4-(trimethylsilyl)but-3-ynoate

HRID 1525337Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1525337
I[C:2](=[CH:7][O:8][CH3:9])[C:3]([O:5][CH3:6])=[O:4].[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])#[CH:11].C(N(CC)CC)C>CN(C=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:9][O:8][CH:7]=[C:2]([C:11]#[C:10][Si:12]([CH3:15])([CH3:14])[CH3:13])[C:3]([O:5][CH3:6])=[O:4]

Komponenten

7

Edukt 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 54067316Methyl 2-iodo-3-methoxyprop-2-enoate

Produkt 1

HCID 53914070Methyl 2-(methoxymethylene)-4-(trimethylsilyl)but-3-ynoateAusbeute 57 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of compound 37-g (30 g, 124 mmol), ethynyltrimethylsilane (24.3 g, 248 mmol), triethylamine (37.6 g, 372 mmol), copper(I) iodide (2.35 g, 6.2 mmol), Pd(dppf)Cl2 (2.50 g) in DMF (300 mL) was stirred overnight at 80° C. The reaction mixture was cooled to room temperature, poured into ice-water, and extracted with ethyl acetate. The organic layer was washed with water, brine, and dried over sodium sulfate and concentrated. The residue was purified by flash chromatography (PE:EA=1:5) to afford compound 37-h (15 g, 57%) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 7.671 (s, 1H), 3.977 (s, 3H), 3.763 (s, 3H), 0.234 (s, 9H); LC-MS (ESI): 213 [M+H]+.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with water, brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (PE:EA=1:5)

Quellen und Nachweise

ORD-Eintrag
ord-0c0335406a8d4591b41d460b8d9b2552
Quelldatensatz
uspto-grants-2015_07
Patentnummer
US09079930B2

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