Triethylamine → HCID 86667832, Verbindung

HRID 869033Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 869033
[C:1]([C:3]1[CH:4]=[C:5]([OH:9])[CH:6]=[CH:7][CH:8]=1)#[CH:2].Br[C:11]1[C:12]([NH2:18])=[N:13][CH:14]=[C:15]([Br:17])[N:16]=1.C(N(CC)CC)C>CN(C=O)C.CCOC(C)=O.[Cl-].[Na+].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>[NH2:18][C:12]1[C:11]([C:2]#[C:1][C:3]2[CH:4]=[C:5]([OH:9])[CH:6]=[CH:7][CH:8]=2)=[N:16][C:15]([Br:17])=[CH:14][N:13]=1

Komponenten

9

Edukt 3

HCID 8471TriethylamineHCID 139144m-EthynylphenolHCID 6200042-Amino-3,5-dibromopyrazine

Produkt 1

HCID 86667832HCID 86667832, VerbindungAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

3-Ethynylphenol (560.5 mg, 310.9 μL, 4.745 mmol) was added dropwise to a solution of 3,5-dibromopyrazin-2-amine (1 g, 3.954 mmol), triethylamine (4.001 g, 5.511 mL, 39.54 mmol), copper (I) iodide (90.37 mg, 0.4745 mmol) and Pd(PPh3)4 (228.5 mg, 0.1977 mmol) in DMF (10 mL) and the resulting solution heated at 120° C. for 3 hours. The reaction mixture was cooled to ambient temperature and diluted with EtOAc and 1 MHCl/brine (1/1) and the layers separated. The aqueous layer was extracted with EtOAc (×2) and the combined organic extracts washed with brine (×2), dried (MgSO4) and concentrated in vacuo. The residue was purified by column chromatography (ISCO Companion™, 120 g column, eluting with 0 to 40% EtOAc/Petroleum Ether, dry loaded) to give the sub-title product as a yellow solid (815 mg, 71% Yield). 1H NMR (400.0 MHz, DMSO) δ 6.88 (dd, 1H), 7.00 (br s, 2H), 7.11-7.11 (m, 1H), 7.17 (d, 1H), 7.25 (t, 1H), 8.12 (s, 1H) and 9.77 (s, 1H) ppm; MS (ES+) 292.0.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. customthe layers separated
  3. extractionThe aqueous layer was extracted with EtOAc (×2)
  4. washthe combined organic extracts washed with brine (×2)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography (ISCO Companion™, 120 g column, eluting with 0 to 40% EtOAc/Petroleum Ether, dry loaded)

Quellen und Nachweise

ORD-Eintrag
ord-434791d2f6c8483e8971ab045ad6d4c0
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08969356B2

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