Binap, (A+-)- → tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoate

HRID 42003Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 42003
[NH2:1][C:2]1[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].[Br:16][C:17]1[CH:22]=[CH:21][C:20](I)=[CH:19][N:18]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.O>[Br:16][C:17]1[N:18]=[CH:19][C:20]([NH:1][C:2]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=2[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:21][CH:22]=1

Komponenten

9

Edukt 4

HCID 634876Binap, (A+-)-HCID 47382712-Bromo-5-iodopyridineHCID 13399998tert-Butyl 2-amino-5-methylbenzoateHCID 23676156Sodium t-butoxide

Produkt 1

HCID 86657255tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoateAusbeute 40,2 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

In a schlenck tube, a mixture of tert-butyl 2-amino-5-methylbenzoate (2.89 mmol, 0.600 g), 2-bromo-5-iodopyridine (2.89 mmol, 0.822 g), BINAP (0.29 mmol, 0.096 g), Pd2(dba)3 (0.14 mmol, 0.132 g) and NaOtBu (5.79 mmol, 0.556 g) in toluene (15 ml) was heated at 120° C. for 3 hours. Water and ethyl acetate were added to the reaction crude. The aqueous phase was extracted again with more ethyl acetate. The organic phase was washed with water and brine, dried, filtered and concentrated in vacuo. The crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%) affording 0.422 g (yield 40%) of the expected product.

Aufarbeitung

  1. extractionThe aqueous phase was extracted again with more ethyl acetate
  2. washThe organic phase was washed with water and brine
  3. customdried
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%)

Quellen und Nachweise

ORD-Eintrag
ord-526c59565f6c4553ab53563a4218665a
Quelldatensatz
uspto-grants-2013_09
Patentnummer
US08536165B2

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