Sodium Carbonate → 3-Bromo-5-(thien-3-yl)benzonitrile

HRID 1452453Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1452453
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([Br:10])[CH:9]=1)[C:5]#[N:6].[S:11]1[CH:15]=[CH:14][C:13](B(O)O)=[CH:12]1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[Na+].[Na+]>C(#N)C.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>[Br:10][C:8]1[CH:7]=[C:4]([CH:3]=[C:2]([C:13]2[CH:14]=[CH:15][S:11][CH:12]=2)[CH:9]=1)[C:5]#[N:6]

Komponenten

7

Edukt 4

HCID 10340Sodium CarbonateHCID 80271Tri-o-tolylphosphineHCID 581760Thiophene-3-boronic acidHCID 27976903,5-Dibromobenzonitrile

Produkt 1

HCID 575262643-Bromo-5-(thien-3-yl)benzonitrile

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A mixture of 3,5-dibromobenzonitrile (3 g, 11.5 mmol), thiophene-3-boronic acid (2.35 g, 18 mmol), dichlorobis(triphenylphosphine)palladium(II)(1.21 g, 1.7 mmol), tri-o-tolylphosphine (0.524 g, 1.7 mmol), sodium carbonate (3.46 g, 33 mmol) in aqueous acetonitrile (1:10), 110 mL) was refluxed under nitrogen for 6 hours, cooled to room temperature, concentrated under reduced pressure, suspended in hydrochloric acid (2N, 50 mL), and extracted with diethyl ether (3×80 mL). The combined organic extracts were washed with water (150 mL), saturated aqueous sodium bicarbonate (150 mL), and brine (50 mL), dried over magnesium sulfate, adsorbed onto silica, chromatographed on silica and eluted with a mobile phase of ethyl acetate in hexane. The first fraction was concentrated under reduced pressure to leave 3-bromo-5-(thien-3-yl)benzonitrile in the form of a yellow amorphous solid. Yield 1.47 g (48 percent). mp 62-63° C.; 1H NMR (CDCl3) δ 7.94 (t, J=1.8 Hz, 1H), 7.79 (t, J=1.5 Hz, 1H), 7.69 (t, J=1.8 Hz, 1H), 7.54 (dd, J1=3.0 Hz, J2=1.5 Hz, 1H), 7.46 (dd, J1=5.1 Hz, J2=3.0 Hz, 1H), 7.34(dd, J1=4.8 Hz, J2=1.5 Hz, 1H); EI/MS 265 m/e (M+); IR (KBr) σ cm−1 2230.

Aufarbeitung

  1. temperaturewas refluxed under nitrogen for 6 hours
  2. concentrationconcentrated under reduced pressure
  3. extractionextracted with diethyl ether (3×80 mL)
  4. washThe combined organic extracts were washed with water (150 mL), saturated aqueous sodium bicarbonate (150 mL), and brine (50 mL)
  5. dry with materialdried over magnesium sulfate
  6. customchromatographed on silica
  7. washeluted with a mobile phase of ethyl acetate in hexane
  8. concentrationThe first fraction was concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-c86bc9f491834cbb923232313f98cf3e
Quelldatensatz
uspto-grants-2009_01
Patentnummer
US07473669B2

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