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Binap, (A+-)- → HCID 24946339, compound

HRID 1667443
Notes
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Reaction equation

HRID 1667443 reaction equation
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].[S:14]1[CH:18]=[CH:17][C:16]([C:19]2[CH:20]=[C:21]([CH:24]=[CH:25][CH:26]=2)[CH2:22][NH2:23])=[CH:15]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+]>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]=[C:19]([C:16]4[CH:17]=[CH:18][S:14][CH:15]=4)[CH:20]=3)[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 634876Binap, (A+-)-HCID 19916941[3-(Thiophen-3-yl)phenyl]methanamineHCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

Product 1

HCID 24946339HCID 24946339, compound

Reagents, catalysts & solvents 3

HCID 9811564
Bis(dibenzylideneacetone)palladium
Catalyst
HCID 8857Ethyl AcetateSolvent
HCID 31374DimethylacetamideSolvent

Procedure

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (150 mg, 0.58 mmol), 3-thiophen-3-yl-benzylamine (122 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-(3-thiophen-3-yl-benzylamino)-2H-phthalazin-1-one: 38 mg (17.8%): m/z (M+H)=368. 1H-NMR (DMSO-d6) δ: 12.34 (s, 1H), 7.93 (d, 1H), 7.84 (m, 1H), 7.75 (m, 1H), 7.64 (m, 3H), 7.52 (dd, 1H), 7.39 (m, 1H), 7.31 (m, 1H), 7.19 (dd, 1H), 6.87 (s, 1H), 4.47 (d, 2H).

Workup

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

Sources & evidence

ORD record
ord-6705f85ad7ae44c1a8f5692af577468d
Source dataset
uspto-grants-2011_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08044041B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes