2-Methyl-3-butyn-2-ol → HCID 58266403, Verbindung

HRID 1888494Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1888494
Br[C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1.[CH3:25][C:26]([OH:30])([C:28]#[CH:29])[CH3:27]>O1CCOCC1.C(Cl)Cl.O.[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>[OH:30][C:26]([CH3:27])([CH3:25])[C:28]#[C:29][C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1

Komponenten

8

Edukt 2

HCID 82582-Methyl-3-butyn-2-olHCID 58266568HCID 58266568, Verbindung

Produkt 1

HCID 58266403HCID 58266403, VerbindungAusbeute 124,2 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
105 °C

Versuchsvorschrift

In a flame dried flask, a mixture of 3-bromo-9-(2-trimethylsilanylethoxymethyl)-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (203 mg, 0.503 mmol) and copper (I) iodide (9.58 mg, 50.3 μmol) in 1,4-dioxane (5.3 mL) was degassed and flushed with nitrogen. Tetrakis(triphenylphosphine)palladium(0) (58.1 mg, 50.3 μmol) and 2-methyl-3-butyn-2-ol (244 μL, 2.52 mmol) were added and the reaction mixture was degassed, purged with nitrogen, and heated at 105° C. for 70 min. The cooled reaction mixture was diluted with DCM and water, the layers separated, and the aqueous phase extracted into DCM. The combined organic phase was dried over sodium sulfate and concentrated in vacuo. The resultant residue was dissolved in EtOAc and absorbed onto silica gel for purification by flash chromatography (silica, 25 g column, Biotage, 1-100% EtOAc in heptane) to afford further title compound as a white-yellow solid (254 mg, 124%). The solid was used without further purification. 1H NMR (DMSO-D6, 400 MHz): 9.33 (s, 1H), 8.98 (s, 1H), 8.91 (d, J=1.9 Hz, 1H), 8.76 (d, J=1.9 Hz, 1H), 6.03 (s, 2H), 5.55 (s, 1H), 3.57 (t, J=7.9 Hz, 2H), 1.51 (s, 6H), 0.82 (t, J=8.0 Hz, 2H), −0.16 (s, 9H).

Aufarbeitung

  1. customIn a flame dried flask
  2. customwas degassed
  3. customflushed with nitrogen
  4. customthe reaction mixture was degassed
  5. custompurged with nitrogen
  6. customThe cooled reaction mixture
  7. customthe layers separated
  8. extractionthe aqueous phase extracted into DCM
  9. dry with materialThe combined organic phase was dried over sodium sulfate
  10. concentrationconcentrated in vacuo
  11. dissolutionThe resultant residue was dissolved in EtOAc
  12. customabsorbed onto silica gel for purification by flash chromatography (silica, 25 g column, Biotage, 1-100% EtOAc in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-c923111efe8f4dfaacfbd49883ecfefc
Quelldatensatz
uspto-grants-2013_08
Patentnummer
US08501765B2

Notizen zur Reaktion

Wird geladen…