Binap, (A+-)- → 4-Chloro-6-(2-chloro-5-trifluoromethyl-benzylamino)-2H-phthalazin-1-one

HRID 1803537

Reaktionsgleichung

Reaktionsgleichung von HRID 1803537
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[NH:7][N:6]=[C:5]2[Cl:13].[Cl:14][C:15]1[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][C:16]=1[CH2:17][NH2:18].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+]>CC(N(C)C)=O.CCOC(C)=O.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]>[Cl:13][C:5]1[C:4]2[C:9](=[CH:10][CH:11]=[C:2]([NH:18][CH2:17][C:16]3[CH:19]=[C:20]([C:23]([F:24])([F:25])[F:26])[CH:21]=[CH:22][C:15]=3[Cl:14])[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

Komponenten

8

Edukt 4

HCID 634876Binap, (A+-)-HCID 27366822-Chloro-5-(trifluoromethyl)benzylamineHCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

Produkt 1

HCID 584472734-Chloro-6-(2-chloro-5-trifluoromethyl-benzylamino)-2H-phthalazin-1-one

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 8857Ethyl AcetateLösungsmittelHCID 31374DimethylacetamideLösungsmittel

Versuchsvorschrift

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (150 mg, 0.58 mmol), 2-chloro-5-trifluoromethyl-benzylamine (135 mg, 0.64 mmol), Pd2(dba)3 (53 mg, 0.058 mmol), rac-BINAP (132 mg, 0.17 mmol) and NaOt-Bu (140 mg, 1.45 mmol) in DMA (6 mL) was heated at 80° C. for 1 h. The mixture was allowed to cool, diluted with EtOAc (25 mL) and washed with water (25 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated. Chromatography on silica (EtOAc/hexanes) yielded the title compound. 4-Chloro-6-(2-chloro-5-trifluoromethyl-benzylamino)-2H-phthalazin-1-one: 18 mg (8.0%): m/z (M+H)=388. 1H-NMR (DMSO-d6) δ: 12.39 (s, 1H), 7.96 (d, 1H), 7.80 (m, 1H), 7.75 (m, 1H), 7.70 (m, 2H), 7.18 (dd, 1H), 6.84 (s, 1H), 4.59 (d, 2H).

Aufarbeitung

  1. temperatureto cool
  2. washwashed with water (25 mL)
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-95ac708ac1324d758399c8ec4ef29957
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08349836B2

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