Binap, (A+-)- → 4-Chloro-6-(2-thiophen-2-yl-benzylamino)-2H-phthalazin-1-one

HRID 1667438

Reaktionsgleichung

Reaktionsgleichung von HRID 1667438
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.[S:15]1[CH:19]=[CH:18][CH:17]=[C:16]1[C:20]1[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=1[CH2:22][NH2:23].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:23][CH2:22][C:21]3[CH:24]=[CH:25][CH:26]=[CH:27][C:20]=3[C:16]3[S:15][CH:19]=[CH:18][CH:17]=3)[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

Komponenten

8

Edukt 4

HCID 634876Binap, (A+-)-HCID 185257241-(2-Thien-2-ylphenyl)methanamine hydrochlorideHCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

Produkt 1

HCID 249463444-Chloro-6-(2-thiophen-2-yl-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-thiophen-2-yl-benzylamine hydrochloride (145 mg, 0.64 mmol), Pd2(dba)3 (53 mg, 0.058 mmol), rac-BINAP (108 mg, 0.17 mmol) and NaOt-Bu (200 mg, 2.1 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-thiophen-2-yl-benzylamino)-2H-phthalazin-1-one: 65 mg (30.5%): m/z (M+H)=368. 1H-NMR (DMSO-d6) δ: 12.34 (s, 1H), 7.91 (d, 1H), 7.64 (m, 2H), 7.47 (m, 2H), 7.37 (m, 2H), 7.25 (dd, 1H), 7.16 (m, 1H), 7.11 (m, 1H), 6.64 (s, 1H), 4.43 (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-d71d56eed8874d4a8c8e32679a33ca2c
Quelldatensatz
uspto-grants-2011_10
Patentnummer
US08044041B2

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