Triethylamine → 6-(1-Dodecynyl)-2-pyridinecarboxaldehyde

HRID 235160

Reaktionsgleichung

Reaktionsgleichung von HRID 235160
Br[C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1.[CH:10]#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21].C(N(CC)CC)C>O1CCCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:10]([C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1)#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21]

Komponenten

8

Edukt 3

HCID 8471Triethylamine2×HCID 698211-Dodecyne3×HCID 27570096-Bromopyridine-2-carbaldehyde

Produkt 1

HCID 183731096-(1-Dodecynyl)-2-pyridinecarboxaldehydeAusbeute 29 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Katalysator2×HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

To a solution of 6-bromo-2-pyridinecarboxaldehyde (3.0 g) in tetrahydrofuran (10 ml), was added sequentially bis(triphenylphosphine)palladium(II) chloride (0.178 g), copper(I)iodide (0.024 g), 1-dodecyne (3.25 ml), and triethylamine (2.12 ml). The solution was stirred at 40° C. overnight. The reaction mixture was cooled to room temperature, charged again with bis(triphenylphosphine)palladium (II) chloride (0.024 g), copper (I) iodide (0.024 g), and triethylamine (2.12 ml), and 1-dodecyne (3.25 ml), and tetrahydrofuran (5.0 ml), and heated at 40° C. for 5 hrs. The reaction mixture was again cooled and recharged as above, and heated at 40° C. for 24 hrs. The cooled mixture was concentrated, taken up in ethyl acetate (100 ml), washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was taken up in ethyl acetate (100 ml) and filtered. The filtrate was combined with material from a similar reaction run 1.43 g of the carboxaldehyde and proportionate amounts of the catalysts, 1-dodecyne, and solvent. The filtrate was concentrated. The residue was purified by flash chromatography using 1.5% ethyl acetate/hexane followed by 1% ethyl acetate/hexane as eluents. The appropriate fractions were collected and concentrated to yield 2.24 g (29%) of product, as an oil.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to room temperature
  2. temperatureheated at 40° C. for 5 hrs
  3. temperatureThe reaction mixture was again cooled
  4. temperatureheated at 40° C. for 24 hrs
  5. concentrationThe cooled mixture was concentrated
  6. washwashed with water and saturated sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. filtrationfiltered
  11. customThe filtrate was combined with material from a similar reaction
  12. concentrationThe filtrate was concentrated
  13. customThe residue was purified by flash chromatography
  14. customThe appropriate fractions were collected
  15. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-8531f43721384aa69de8006ccfdf860e
Quelldatensatz
uspto-grants-1997_01
Patentnummer
US05597838

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