Binap, (A+-)- → Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

HRID 446314Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 446314
Cl[C:2]1[C:7]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][N:9]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[NH2:14][C:15]1[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=1[C:26]([F:29])([F:28])[F:27])[C:18]([O:20][CH2:21][CH3:22])=[O:19].CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:11]1[CH:12]=[CH:13][C:8]([C:7]2[C:2]([NH:14][C:15]3[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=3[C:26]([F:27])([F:28])[F:29])[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[N:3][CH:4]=[CH:5][CH:6]=2)=[N:9][CH:10]=1

Komponenten

8

Edukt 4

HCID 634876Binap, (A+-)-HCID 161089744-(2-Chloropyridin-3-yl)pyrimidineHCID 19783159Ethyl 3-amino-4-(trifluoromethyl)benzoateHCID 23676156Sodium t-butoxide

Produkt 1

HCID 66970285Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

4-(2-Chloropyridin-3-yl)pyrimidine (1.5 g, 7.8 mmol), ethyl 3-amino-4-(trifluoromethyl)benzoate (2.0 g, 8.6 mmol), Sodium tert-butoxide (1.1 g, 12 mmol), rac-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (0.49 g, 0.78 mmol) were all mixed together in toluene (25 ml) and degassed under vacuum. Nitrogen was bubbled into the reaction for 5 minutes and then Palladium (II) acetate (0.088 g, 0.39 mmol) was added. The mixture was heated to 80° C. and stirred overnight. The reaction was diluted with ethyl acetate and washed with an aqueous saturated solution of sodium bicarbonate, water and brine. The organic layer was then dried with sodium sulfate and purified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes to afford ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate as a brown solid. MS m/z=389 [M+1]+. Calc'd for C19H15F3N4O2: 388.11.

Aufarbeitung

  1. customdegassed under vacuum
  2. customNitrogen was bubbled into the reaction for 5 minutes
  3. washwashed with an aqueous saturated solution of sodium bicarbonate, water and brine
  4. dry with materialThe organic layer was then dried with sodium sulfate
  5. custompurified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-f176647a0d194514a51ae28998697137
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08476434B2

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