Triethylamine → 3-Bromo-5-(prop-1-yn-1-yl)pyridine

HRID 1468223Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1468223
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1.C[Si](C)(C)[C:11]#[C:12][CH3:13].C(N(CC)CC)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1(C)C=CC=CC=1.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Br:8][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([C:11]#[C:12][CH3:13])[CH:7]=1

Komponenten

9

Edukt 4

HCID 8471TriethylamineHCID 693693,5-DibromopyridineHCID 803631-(Trimethylsilyl)prop-1-yneHCID 2724141Tetrabutylammonium Fluoride

Produkt 1

HCID 574665963-Bromo-5-(prop-1-yn-1-yl)pyridineAusbeute 66 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Versuchsvorschrift

3,5-Dibromopyridine (30 g, 127 mmol), copper(I) iodide (7.24 g, 38.0 mmol) and tetrakis(triphenylphosphine)palladium(0) (4.39 g, 3.80 mmol) were mixed in toluene (120 mL) under nitrogen atmosphere. 1-(Trimethylsilyl)-1-propyne (26.36 mL, 164.5 mmol), triethylamine (53.0 mL, 380 mmol) and tetra-n-butylammonium fluoride (12.66 mL, 12.66 mmol) were added. The mixture was heated to reflux and stirred under nitrogen overnight. Water (100 mL) was added to the reaction mixture was filtered and the phases separated. The organic phase was washed with 1 M HCl aq. (100 mL). The organic phase was concentrated and dissolved in MeOH (200 mL), filtered and concentrated. The mixture was dissolved in DCM and evaporated with silica gel to dryness, and then transferred to a silica gel column (300 g). The product was eluted with a gradient of EtOAc (0-5%) in heptane. The fractions containing the pure product was combined and evaporated to give the title compound (16.39 g, 66% yield): 1H NMR (500 MHz, CDCl3) δ ppm 2.08 (s, 3 H), 7.82 (t, 1 H), 8.52 (d, 1 H), 8.55 (d, 1 H); MS (APCI+) m/z 197.0 [M+H]+.

Aufarbeitung

  1. temperatureThe mixture was heated
  2. temperatureto reflux
  3. filtrationwas filtered
  4. customthe phases separated
  5. washThe organic phase was washed with 1 M HCl aq. (100 mL)
  6. concentrationThe organic phase was concentrated
  7. dissolutiondissolved in MeOH (200 mL)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. dissolutionThe mixture was dissolved in DCM
  11. customevaporated with silica gel to dryness
  12. washThe product was eluted with a gradient of EtOAc (0-5%) in heptane
  13. additionThe fractions containing the pure product
  14. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-9f74c9db3bea4b1ca6afb7562e255b22
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09000184B2

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