Methyl 4-bromobenzoate → Methyl 4'-[(6-fluoro-1,3-benzothiazol-2-yl)amino]biphenyl-4-carboxylate

HRID 2356803Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2356803
B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.Br[C:20]1[CH:29]=[CH:28][C:23]([C:24]([O:26][CH3:27])=[O:25])=[CH:22][CH:21]=1.CC([O-])=O.[K+].Br[C:36]1[CH:41]=[CH:40][C:39]([NH:42][C:43]2[S:44][C:45]3[CH:51]=[C:50]([F:52])[CH:49]=[CH:48][C:46]=3[N:47]=2)=[CH:38][CH:37]=1.C([O-])(O)=O.[Na+]>CN(C=O)C.CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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>[F:52][C:50]1[CH:49]=[CH:48][C:46]2[N:47]=[C:43]([NH:42][C:39]3[CH:40]=[CH:41][C:36]([C:20]4[CH:29]=[CH:28][C:23]([C:24]([O:26][CH3:27])=[O:25])=[CH:22][CH:21]=4)=[CH:37][CH:38]=3)[S:44][C:45]=2[CH:51]=1

Komponenten

10

Edukt 5

HCID 12081Methyl 4-bromobenzoateHCID 516892Sodium BicarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 7147099N-(4-bromophenyl)-6-fluoro-1,3-benzothiazol-2-amine

Produkt 1

HCID 58270607Methyl 4'-[(6-fluoro-1,3-benzothiazol-2-yl)amino]biphenyl-4-carboxylateAusbeute 18 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of bis(pinacolato)diboron (0.35 g, 1.4 mmol), methyl 4-bromobenzoate (0.30 g, 1.4 mmol), palladium(II) acetate (0.01 g, 0.04 mmol), and KOAc (0.41 g, 4.2 mmol) in DMF (7.5 mL) was degassed with argon for 30 min at rt. The mixture was then heated at 80° C. for 4 h. After the mixture was cooled to rt, N-(4-bromophenyl)-6-fluoro-1,3-benzothiazol-2-amine (0.45 g, 1.4 mmol), tetrakis(triphenylphosphine)palladium(0) (0.05 g, 0.04 mmol), and saturated aqueous NaHCO3 (5 mL) were added. The mixture was heated at 85° C. overnight. Upon cooling to rt, the mixture was diluted with EtOAc. The combined organic phases were separated, dried over Na2SO4, and concentrated in vacuo. Purification by column chromatography (25% EtOAc in hexanes) yielded 0.094 g (18%) of the title compound. LC/MS m/z 379.3 (MH+); retention time 3.87 min. 1H NMR (400 MHz, CD3OD) δ 3.93 (s, 3H), 7.05 (t, 1H), 7.39-7.81 (m, 8H), 8.03 (d, 2H).

Aufarbeitung

  1. customwas degassed with argon for 30 min at rt
  2. temperatureAfter the mixture was cooled to rt
  3. temperatureThe mixture was heated at 85° C. overnight
  4. temperatureUpon cooling to rt
  5. customThe combined organic phases were separated
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated in vacuo
  8. customPurification by column chromatography (25% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-ebf7fe45967a444081f0e5a120c008e1
Quelldatensatz
uspto-grants-2010_07
Patentnummer
US07759376B2

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