4-(Hydroxymethyl)benzeneboronic acid → HCID 86653489, Verbindung

HRID 1505841Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1505841
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.[OH:25][CH2:26][C:27]1[CH:32]=[CH:31][C:30](B(O)O)=[CH:29][CH:28]=1>C(#N)C.[F-].[K+].O>[OH:25][CH2:26][C:27]1[CH:32]=[CH:31][C:30]([C:24]2[CH:2]=[CH:3][C:4]3[C:8]4[CH:9]=[C:10]([C:13]#[N:14])[N:11]=[CH:12][C:7]=4[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:5]=3[N:23]=2)=[CH:29][CH:28]=1

Komponenten

6

Edukt 2

HCID 27347064-(Hydroxymethyl)benzeneboronic acidHCID 58266568HCID 58266568, Verbindung

Produkt 1

HCID 86653489HCID 86653489, VerbindungAusbeute 172,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittelHCID 522689Potassium FluorideLösungsmittel

Reaktionsbedingungen

Temperatur
140 °C

Versuchsvorschrift

A mixture of 3-bromo-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (700 mg, 0.87 mmol), 4-hydroxymethylbenzeneboronic acid (400 mg, 1.32 mmol) and 1,1′-[bis(diphenylphosphino)ferrocene]dichloropalladium(II) (52.5 mg, 0.064 mmol) in acetonitrile (21 mL) and 2N aqueous potassium fluoride solution (21 mL) was divided equally across two 25 mL microwave vials. Each vial was degassed with nitrogen for 10 minutes before the mixtures were heated under microwave irradiation at 140° C. for 30 minutes. The reaction mixtures were allowed to cool to ambient temperature, combined and diluted with water (50 mL). The precipitate was collected by filtration, washed with water (50 mL) and left to air dry. The resultant grey solid was purified by flash column chromatography (silica, 40 g column, ISCO, 0-100% ethyl acetate in cyclohexane). The isolated solid was then triturated with hot t-BME to afford the title compound as a light grey solid (646 mg, 26%). LCMS (Method B): RT=4.11 min, M+H+=431.

Aufarbeitung

  1. customEach vial was degassed with nitrogen for 10 minutes before the mixtures
  2. customThe reaction mixtures
  3. temperatureto cool to ambient temperature
  4. filtrationThe precipitate was collected by filtration
  5. washwashed with water (50 mL)
  6. waitleft to air
  7. customdry
  8. customThe resultant grey solid was purified by flash column chromatography (silica, 40 g column, ISCO, 0-100% ethyl acetate in cyclohexane)
  9. customThe isolated solid was then triturated with hot t-BME

Quellen und Nachweise

ORD-Eintrag
ord-54133c5b0182462898f0aa0167373b85
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09216980B2

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