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

HRID 1803536

反応式

HRID 1803536 の反応式
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:16]=[CH:17][C:18]([CH3:23])=[C:19]([CH:22]=1)[CH2:20][NH2:21].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:21][CH2:20][C:19]3[CH:22]=[C:15]([Cl:14])[CH:16]=[CH:17][C:18]=3[CH3:23])[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

参加物

8

反応物 4

HCID 634876Binap, (A+-)-HCID 27576735-Chloro-2-methylbenzylamineHCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

生成物 1

HCID 249461624-Chloro-6-(5-chloro-2-methyl-benzylamino)-2H-phthalazin-1-one

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒HCID 31374Dimethylacetamide溶媒

実験手順

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (150 mg, 0.58 mmol), 5-chloro-2-methyl-benzylamine (100 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-(5-chloro-2-methyl-benzylamino)-2H-phthalazin-1-one: 20 mg (10.3%): m/z (M+H)=334. 1H-NMR (DMSO-d6) δ: 12.63 (s, 1H), 8.21 (d, 1H), 7.78 (m, 1H), 7.56 (m, 1H), 7.50 (m, 2H), 7.42 (dd, 1H), 7.10 (s, 1H), 4.66 (d, 2H), 2.60 (s, 3H).

後処理

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

出典と根拠

ORDレコード
ord-86a677dad01344c6b1438d75b3de2f57
出典データセット
uspto-grants-2013_01
特許番号
US08349836B2

関連ノート

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