Trimethylsilylacetylene → 5-Nitro-3-trimethylsilanylethynyl-pyridin-2-ylamine

HRID 1515845

Reaktionsgleichung

Reaktionsgleichung von HRID 1515845
[NH2:1][C:2]1[C:7](I)=[CH:6][C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14]>C(N(CC)CC)C.O1CCCC1.CN(C)C(=O)C.[Cu]I.C1(P([Pd-](Cl)P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[N+:9]([C:5]1[CH:6]=[C:7]([C:17]#[C:16][Si:13]([CH3:15])([CH3:14])[CH3:12])[C:2]([NH2:1])=[N:3][CH:4]=1)([O-:11])=[O:10]

Komponenten

8

Edukt 2

HCID 66111TrimethylsilylacetyleneHCID 116231122-Amino-3-iodo-5-nitropyridine

Produkt 1

HCID 115287895-Nitro-3-trimethylsilanylethynyl-pyridin-2-ylamineAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178479804HCID 178479804, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 8471TriethylamineLösungsmittelHCID 31374DimethylacetamideLösungsmittel

Versuchsvorschrift

2-Amino-3-iodo-5-nitropyridine (10.0 g, 37.75 mmol) was dissolved in a mixture of triethylamine (250 mL), tetrahydrofuran (40 mL), N,N-dimethylacetamide (80 mL) and the solution was degassed and purged with nitrogen. Trimethylsilylacetylene (8.0 mL, 56.5 mmol), copper(I) iodide (0.145 g, 0.75 mmol) and bis(triphenylphosphino) palladium (II) chloride (0.53 g, 0.75 mmol) were added. The mixture was degassed and purged with nitrogen one more time, then stirred at ambient temperature for 16 h. The precipitate was removed by filtration, and the filtrate was concentrated in vacuo. The residue was purified by flash column chromatography (silica gel from QingDao, 200-300 mesh, 15%-35% ethyl acetate/hexanes) to afford 5-nitro-3-trimethylsilanylethynyl-pyridin-2-ylamine (6.2 g, 70%) as a yellow solid: LC/MS m/e calcd for C10H13N3O2Si [M+H]+ 236.32, observed 236.0.

Aufarbeitung

  1. customthe solution was degassed
  2. custompurged with nitrogen
  3. customThe mixture was degassed
  4. custompurged with nitrogen one more time
  5. customThe precipitate was removed by filtration
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe residue was purified by flash column chromatography (silica gel from QingDao, 200-300 mesh, 15%-35% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-d69067af30874b68b609adb255ea63d3
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08222416B2

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